Cross Reference to Related Applications
[0001] The present application claims priority of
Chinese patent application No. 201910159559.1, titled "process and system for producing
light olefins from inferior oils", filed on March 4, 2019,
Chinese patent application No. 201910159576.5, titled "upgrading process and system
for producing light olefins from inferior oils", filed on March 4, 2019, and
Chinese patent application No. 201910159674.9, titled "process and system for producing
propylene and high octane gasoline from inferior oils", filed on March 4, 2019, which is incorporated herein by reference in its entirety.
Technical Field
[0002] The present application relates to catalytic conversion of hydrocarbon oils, particularly
to a process and system for producing light olefins by carrying out catalytic cracking
on inferior oils after catalytic upgrading in the presence of hydrogen.
Background Art
[0003] Light olefins represented by ethylene and propylene are the most basic raw materials
used in chemical industry. Currently, about 98% of the ethylene produced around the
world comes from steam cracking technology, with naphtha accounting for 46% and ethane
accounting for 34% of the feedstocks used for ethylene production. About 62% of the
propylene comes from the co-production with ethylene by steam cracking. The steam
cracking technology has become substantially perfect, is a process of consuming a
large amount of energy, and is limited by using high-temperature resistant materials,
and thus has little potential for further improvement.
[0004] With the slow recovery of the world economy, the increase of oil demand is slowed
down, and the supply and demand of the world oil market are basically kept loose.
The international energy agency believes that, on the supply side, the crude oil production
will continue to rise in Non-OPEC countries including the United States in the coming
years, and the global crude oil demand will be tightened in 2022; on the demand side,
the global crude oil demand will continuously rise in the next 5 years, and the demand
may be over 1 hundred million barrels per day in 2019; among them, the amount of unconventional
oils and inferior heavy oils to be processed is increasing year by year. Therefore,
the process for producing chemical raw materials such as light olefins to the maximum
extent from unconventional oils or inferior oils is the key point for broadening the
source of the raw materials for producing light olefins, adjusting the product structure,
and improving the quality of products and enhancing the efficiency in petrochemical
enterprises.
[0005] Chinese patent application publication
CN101045884A discloses a process for producing clean diesel and light olefins from residual oil
and heavy distillate oil. In the process, residual oil and an optional catalytic cracking
slurry oil are fed to a solvent deasphalting unit, the obtained deasphalted oil and
an optional heavy distillate oil are fed to a hydrogenation unit and subjected to
hydrocracking reaction in the presence of hydrogen, and the products are separated
to obtain light and heavy naphtha fractions, diesel oil fraction and hydrogenated
tail oil; the hydrogenated tail oil is fed to a catalytic cracking unit to carry out
catalytic cracking reaction, and the product is separated to obtain light olefins,
gasoline fraction, diesel oil fraction and slurry oil; the diesel oil is recycled
to the catalytic cracking unit, and all or part of the slurry oil is returned to the
solvent deasphalting unit. The process is used to process a mixture of vacuum residue
and catalytic cracking slurry oil to yield 27.3 wt% propylene and 10.6 wt% ethylene.
[0006] International application publication
WO2015084779A1 discloses a process for producing light olefins, particularly propylene, using a
combination of solvent deasphalting and high severity catalytic cracking. The process
comprises the following steps: mixing a vacuum residue and a solvent, and then performing
a solvent deasphalting treatment to obtain deasphalted oil rich in the solvent and
deoiled asphalt; the deasphalted oil rich in solvent is fed to a heavy oil deep catalytic
cracking device for deep cracking reaction after separating the solvent, to obtain
a target product rich in light olefins, especially propylene. In the process, the
residual oil is first subjected to solvent deasphalting treatment, and then the deasphalted
oil is efficiently converted to produce light olefins through a combined process,
but the deoiled asphalt is not used or processed.
[0007] Chinese patent publication
CN106701185B discloses a residual oil treatment process, comprising a solvent deasphalting device,
a hydrogenation pretreatment reaction zone, a hydrotreating reaction zone and a catalytic
cracking reaction zone; the process comprises the following steps: separating a residual
oil feedstock by fractionation to obtain a light fraction and a heavy fraction, treating
the heavy fraction in a solvent deasphalting device to obtain deasphalted oil and
deoiled asphalt, mixing the light fraction, the deasphalted oil and hydrogen, passing
the resulted mixture sequentially through a hydrogenation pretreatment reaction zone
and a hydrotreating reaction zone connected in series, subjecting the reaction effluent
from the hydrotreating reaction zone to gas-liquid separation, recycling the resulting
gas phase to the hydrogenation pretreatment reaction zone and/or the hydrotreating
reaction zone, feeding the resulting liquid phase directly into a catalytic cracking
reaction zone to carry out catalytic cracking reaction, and separating the catalytic
cracking reaction effluent to obtain dry gas, liquefied gas, a catalytic cracking
gasoline fraction, a catalytic cracking diesel fraction, a catalytic cracking heavy
cycle oil and a catalytic cracking slurry oil. The process of the patent can prolong
the stable operation period of the device.
[0008] Chinese patent publication
CN1171978C discloses a process for the conversion of high-sulfur high-metal residual oils, in
which deasphalted oil obtained by extracting residual oil and slurry oil with a solvent,
a heavy cycle oil and an optional solvent refining extract oil are fed into a hydrotreatment
device together, and reacted in the presence of hydrogen and a hydrogenation catalyst,
and the product is separated to obtain gas, naphtha, hydrogenated diesel oil and hydrogenated
tail oil, in which the hydrogenated tail oil is fed into a catalytic cracking device,
and subjected to cracking reaction in the presence of cracking catalyst, and the reaction
product is separated, in which the resulting heavy cycle oil can be recycled to the
hydrotreatment device, and the resulting slurry oil is recycled to the solvent deasphalting
device. The process can reduce the investment and operation cost of the hydrotreatment
device, and improve the yield and quality of the light oil.
[0009] In order to obtain more light olefins from inferior oils, the prior art adopts a
technology combining solvent deasphalting and hydrotreatment to provide a high-quality
feedstock for catalytic cracking, but the yield of deasphalted oil is low, and the
benefit is limited from the viewpoint of economy of the whole process, and in addition,
the deoiled asphalt is not well utilized. Consequently, the utilization rate of the
inferior oil in the prior art is low, and more pitches are still generated. Thus,
there is a need to develop a green and efficient conversion technology for producing
light olefins from inferior oils, so as to increase the utilization rate of the inferior
oil and to produce more ethylene, propylene and the like with high added values.
Summary of the Invention
[0010] An object of the present application is to provide a process and system for producing
light olefins from inferior oils. The process and system can realize green and efficient
conversion of inferior oils and can also realize the production of chemical raw materials,
namely light olefins, from inferior oils.
[0011] In order to achieve the above object, in an aspect, the present application provides
a process for producing light olefins from inferior oils, comprising the steps of:
- 1) subjecting an inferior oil feedstock to a thermal conversion reaction in the presence
of hydrogen to obtain a conversion product;
- 2) subjecting the conversion product to a first separation to obtain a first separated
product, wherein in the first separated product, the content of components having
a boiling point below 350 °C is not greater than about 5 wt%, and the content of components
having a boiling point between 350 °C and 524 °C is about 20-60 wt%;
- 3) subjecting the first separated product to a second separation selected from vacuum
distillation, solvent extraction or a combination thereof to obtain an upgraded oil
and a pitch;
- 4) subjecting the upgraded oil obtained in step 3) to hydro-upgrading to obtain a
hydro-upgraded oil;
- 5) subjecting the hydro-upgraded oil obtained in step 4) to a third separation to
obtain a hydro-upgraded heavy oil;
- 6) subjecting the hydro-upgraded heavy oil obtained in step 5) to catalytic cracking
to obtain a catalytic cracking product comprising a light olefin; and
- 7) optionally, recycling at least a part of the pitch obtained in step 3) to step
1) for the thermal conversion reaction.
[0012] In another aspect, the present application also provides a system for producing light
olefins from inferior oils, comprising a thermal conversion reaction unit, a first
separation unit, a second separation unit, a hydro-upgrading unit, a third separation
unit and a catalytic cracking unit, wherein:
the thermal conversion reaction unit is configured to carry out a thermal conversion
reaction on an inferior oil feedstock in the presence of hydrogen to obtain a conversion
product;
the first separation unit is configured to separate the conversion product to obtain
a first separated product, wherein in the first separated product, the content of
components having a boiling point below 350 °C is not greater than about 5 wt%, and
the content of components having a boiling point between 350 °C and 524 °C is about
20-60 wt%;
the second separation unit is configured to separate the first separated product into
an upgraded oil and a pitch, and is selected from a vacuum distillation unit, a solvent
extraction unit or a combination thereof;
the hydro-upgrading unit is configured to carry out hydro-upgrading reaction on the
upgraded oil to obtain a hydro-upgraded oil;
the third separation unit is configured to separate the hydro-upgraded oil to obtain
a hydro-upgraded heavy oil; and
the catalytic cracking unit is configured to carry out catalytic cracking reaction
on the hydro-upgraded heavy oil to obtain a catalytic cracking product comprising
a light olefin.
[0013] The process and system of the present application provide one or more of the following
advantages over the prior art:
- 1. The processing of inferior oils with high metal and high asphaltene content, a
high-efficiency conversion of inferior oil feedstocks, and a great reduction of the
pitch amount can be achieved. Preferably, the overall conversion of the inferior oil
feedstock can be greater than 90 wt%, or even greater than 95 wt%, and the amount
of discarded pitch can be less than 10 wt%, or even less than 5 wt%.
- 2. The process and system of the present application optimize the distillation range
and composition of the material to be subjected to the second separation, and allow
an easy operation of the second separation process.
- 3. The present application allows a high efficiency upgrading of inferior oil feedstocks
and provides an upgrading oil rich in saturated structure and substantially free of
heavy metal and asphaltene for catalytic cracking units. Preferably, the resulting
upgraded oil may have a heavy metal content (calculated as the total weight of nickel
and vanadium) of less than 10 µg/g, or even less than 5 µg/g, and the upgraded oil
may have an asphaltene content of less than 2.0 wt%, or even less than 0.5 wt%.
- 4. The present application allows further processing of the upgraded oil to produce
chemical raw materials, namely light olefins, and the yield of light olefins can be
more than 36%.
[0014] Other characteristics and advantages of the present application will be described
in detail in the detailed description hereinbelow.
Brief Description of the Drawings
[0015] The drawings, forming a part of the present description, are provided to help the
understanding of the present application, and should not be considered to be limiting.
The present application can be interpreted with reference to the drawings in combination
with the detailed description hereinbelow. In the drawings:
FIG. 1a shows a schematic diagram of a preferred embodiment of the process and system
of the present application;
FIG. 1b shows a schematic diagram of another preferred embodiment of the process and
system of the present application;
FIG. 2a shows a schematic diagram of another preferred embodiment of the process and
system of the present application;
FIG. 2b shows a schematic diagram of another preferred embodiment of the process and
system of the present application.
Description of the reference numerals
| 1 |
pipeline |
2 |
pipeline |
3 |
pipeline |
| 4 |
pipeline |
5 |
pipeline |
6 |
thermal conversion reactor |
| 7 |
pipeline |
8 |
high pressure separation unit |
9 |
pipeline |
| 10 |
pipeline |
11 |
pipeline |
12 |
low pressure separation |
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unit |
| 13 |
pipeline |
14 |
pipeline |
15 |
pipeline |
| 16 |
pipeline |
17 |
second separation unit |
18 |
pipeline |
| 19 |
pipeline |
20 |
pipeline |
21 |
pipeline |
| 22 |
pipeline |
23 |
hydro-upgrading unit |
24 |
pipeline |
| 25 |
pipeline |
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pipeline |
27 |
pipeline |
| 28 |
pipeline |
29 |
first reaction zone |
30 |
second reaction zone |
| 31 |
pipeline |
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stripping section |
33 |
disengager |
| 34 |
cyclone separator |
35 |
gas collection chamber |
36 |
vapor line |
| 37 |
spent catalyst standpipe |
38 |
spent catalyst slide valve |
39 |
regenerator |
| 40 |
cyclone separator |
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flue gas pipeline |
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pipeline |
| 43 |
air distributor |
44 |
pipeline |
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pipeline |
| 46 |
degassing tank |
47 |
pipeline |
48 |
regenerated catalyst standpipe |
| 49 |
regenerated catalyst slide valve |
50 |
pipeline |
51 |
pipeline |
| 52 |
pipeline |
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pipeline |
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pipeline |
| 55 |
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| 58 |
separator |
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Detailed Description of the Invention
[0016] The present application will be further described hereinafter in detail with reference
to particular embodiments thereof and the accompanying drawings. It should be noted
that the particular embodiments of the present application are provided for illustration
purpose only, and are not intended to be limiting in any manner.
[0017] In the context of the present application, the boiling point, boiling range (sometimes
also referred to as distillation range), end boiling point and initial boiling point
or similar parameters disclosed herein are all measured at atmospheric pressure (101325
Pa).
[0018] In the context of the present application, unless otherwise specified, the pressures
given are all gauge pressures.
[0019] All publications, patent applications, patents, and other references cited herein
are hereby incorporated by reference in their entirety.
[0020] Unless otherwise stated, the terms used herein have the same meaning as commonly
understood by the person skilled in the art; and if the terms are defined herein and
their definitions are different from the ordinary understanding in the art, the definition
provided herein shall prevail.
[0021] Where a material, substance, process, step, device, component or the like is modified
using "commonly used in the art", "commonly known in the art", or similar expressions,
the subject matter modified by such an expression is intended to encompass not only
those commonly used or known in the art at the time of the filing of the present application,
but also those not commonly used or known at present but will become well known in
the art to be useful for a similar purpose.
[0022] Unless otherwise specified, all percentages, parts, ratios, etc. disclosed herein
are expressed on a weight basis, unless such an interpretation is in conflict with
the general understanding of those of skill in the art.
[0023] Any specific numerical value, including the endpoints of a numerical range, described
in the context of the present application is not restricted to the exact value thereof,
but should be interpreted to further encompass all values close to said exact value.
Moreover, regarding any numerical range described herein, arbitrary combinations can
be made between the endpoints of the range, between each endpoint and any specific
value within the range, or between any two specific values within the range, to provide
one or more new numerical range(s), where said new numerical range(s) should also
be deemed to have been specifically described in the present application.
[0024] In the context of the present application, in addition to those matters explicitly
stated, any matter or matters not mentioned are considered to be the same as those
known in the art without any change. Moreover, any of the embodiments described herein
can be freely combined with another one or more embodiments described herein, and
the technical solutions or ideas thus obtained are considered as part of the original
disclosure or original description of the present application, and should not be considered
to be a new matter that has not been disclosed or anticipated herein, unless it is
clear to the person skilled in the art that such a combination is obviously unreasonable.
[0025] In a first aspect, the present application provides a process for producing light
olefins from inferior oils, comprising the steps of:
- 1) subjecting an inferior oil feedstock to a conversion reaction in the presence of
hydrogen to obtain a conversion product;
- 2) subjecting the conversion product to a first separation to obtain a first separated
product, wherein in the first separated product, the content of components having
a boiling point below 350 °C is not greater than about 5 wt%, and the content of components
having a boiling point between 350 °C and 524 °C is about 20-60 wt%;
- 3) subjecting the first separated product to a second separation selected from vacuum
distillation, solvent extraction or a combination thereof to obtain an upgraded oil
and a pitch;
- 4) subjecting the upgraded oil obtained in step 3) to hydro-upgrading to obtain a
hydro-upgraded oil;
- 5) subjecting the hydro-upgraded oil obtained in step 4) to a third separation to
obtain a hydro-upgraded heavy oil;
- 6) subjecting the hydro-upgraded heavy oil obtained in step 5) to catalytic cracking
reaction to obtain a catalytic cracking product comprising a light olefin; and
- 7) optionally, recycling at least a part of the pitch obtained in step 3) to step
1) for conversion reaction.
[0026] The process of the present application can maintain the long-term operation of the
system while reducing discarded pitch as much as possible and improving the utilization
rate of resources, in which the conversion reaction and each separation step are the
key point that determines whether the system can be operated for a long time or not,
and the conversion rate of the conversion reaction is very important for the stability
control of the system and the stability of the separation operation. The inventors
have found after extensive experiments that in the conversion reaction the conversion
rate of components having a boiling point above 524 °C in the inferior oil (also referred
to herein as "conversion rate of the conversion reaction") may be in a range of about
30-70 wt%, preferably about 30-60 wt%, wherein the conversion rate = (weight of components
having a boiling point above 524 °C in the inferior oil - weight of components having
a boiling point above 524 °C in the conversion product)/weight of components having
a boiling point above 524 °C in the inferior oil ×100 wt%.
[0027] According to the present application, said conversion reaction of step 1) is essentially
a thermal conversion reaction, in which macromolecules of the inferior oil, especially
asphaltene aggregates, are subjected to disaggregation of asphaltene aggregates, cracking
of macromolecules and removal of heteroatoms S, N, and said thermal conversion reaction
brings about a conversion rate of components having a boiling point above 524 °C in
the inferior oil in a range of about 30-70 wt%, preferably about 30-60 wt%. There
is no strict requirement on the conditions (including the catalyst) and reactor used
in the present application for conversion reaction, as long as the above conversion
rate can be achieved.
[0028] According to the present application, the conversion reaction may be carried out
in the presence or absence of a conversion catalyst. In a preferred embodiment, the
conversion reaction is carried out in the presence of a conversion catalyst, which
may comprise at least one selected from the group consisting of Group VB metal compounds,
Group VIB metal compounds, and Group VIII metal compounds, preferably at least one
of Mo compounds, W compounds, Ni compounds, Co compounds, Fe compounds, V compounds,
and Cr compounds. Further preferably, the conversion catalyst is not a supported catalyst,
and may be for example a dispersed catalyst. For example, the conversion catalyst
may be selected from the group consisting of a solid material comprising a sulfide
of the above-mentioned metal, an organic complex or chelate comprising the above-mentioned
metal, or an aqueous solution comprising an oxide of the above-mentioned metal. In
particular, the conversion catalyst may be, for example, an organo-metal complex/chelate
such as one or more of molybdenum octoate, molybdenum naphthenate, nickel naphthenate,
tungsten naphthenate, iron oleate, molybdenum dialkylthioformate, etc.; or solid powder
comprising an oxide and/or sulfide of the above-mentioned metal, such as one or more
of hematite, molybdenite, molybdenum sulfide, iron sulfide, etc.; or an aqueous solution
containing an oxide of the above-mentioned metal and/or an inorganic acid salt capable
of decomposing to produce an oxide of the above-mentioned metal, for example, an aqueous
solution of ammonium molybdate, molybdenum sulfate, molybdenum nitrate, nickel nitrate,
cobalt nitrate, molybdenum oxide, iron oxide, nickel oxide, tungsten oxide, vanadium
oxide, etc.. The conversion catalyst is present in the reaction system in a highly
dispersed form with a particle size of from about 2 nm to about 50 µm, preferably
from about 2 nm to about 1 µm.
[0029] In a preferred embodiment, said conversion reaction of step 1) is carried out in
a slurry bed reactor, in which the liquid reactant is reacted in the presence of a
catalyst that is present in the form of a solid suspension.
[0030] In a preferred embodiment, the conversion reaction may be carried out under conditions
including: a temperature of about 380-470 °C, preferably about 400-440 °C; a hydrogen
partial pressure of about 10-25 MPa, preferably about 13-20 MPa; a volume space velocity
of the inferior oil of about 0.01-2 h
-1, and preferably about 0.1-1.0 h
-1; a volume ratio of hydrogen to the inferior oil of about 500-5000, preferably about
800-2000, and an amount of the conversion catalyst of about 10-50000 µg/g, preferably
about 30-25000 µg/g calculated on the basis of the active metal in the conversion
catalyst and relative to the weight of the inferior oil.
[0031] According to the present application, the inferior oil may be selected from low quality
feedstock oil containing asphaltenes, where said asphaltenes refer to materials in
the feedstock oil that are not soluble in non-polar, small molecular n-alkanes (such
as n-pentane or n-heptane) but soluble in benzene or toluene. Preferably, the inferior
oil meets one or more of the following criteria: an API value of less than about 27,
a boiling point greater than about 350 °C (preferably greater than about 500 °C, more
preferably greater than about 524 °C), an asphaltene content greater than about 2
wt% (preferably greater than about 5 wt%, more preferably greater than about 10 wt%,
still more preferably greater than about 15 wt%), and a heavy metal content greater
than about 100 µg/g, calculated as the total weight of nickel and vanadium. In certain
embodiments, the inferior oil may be at least one selected from the group consisting
of inferior crude oil, heavy oil, deoiled asphalt, coal derived oil, shale oil, and
petrochemical waste oil. Other low-quality feedstock oil well known to those skilled
in the art can be used alone or in mixture as the inferior oil feedstock for conversion
reaction, of which the detailed description is omitted herein for brevity.
[0032] According to the present application, the "inferior crude oil" can be "thick oil",
where the "thick oil" refers to crude oil with high content of asphaltene and resin
and high viscosity, and a crude oil with a density of more than 0.943 g/cm
3 at 20 °C on the ground and a crude oil viscosity of more than 50 centipoises underground
is normally referred to as a thick oil.
[0033] According to the present application, the "heavy oil" refers to distillate oil or
residual oil having a boiling point above 350 °C, where the "distillate oil" generally
refers to distillate products obtained by atmospheric distillation and vacuum distillation
of crude oil or secondary processing oil, such as heavy diesel oil, heavy gas oil,
lubricating oil fraction or cracking feedstock and the like; the "residual oil" refers
to bottoms obtained by atmospheric and vacuum distillation of crude oils, and normally
bottoms obtained by atmospheric distillation are referred to as atmospheric residue
(typically a fraction having a boiling point above 350 °C) and bottoms obtained by
vacuum distillation are referred to as vacuum residue (typically a fraction having
a boiling point above 500 °C or 524 °C). The residual oil may be at least one selected
from the group consisting of topped crude oil, heavy oil obtained from oil sand bitumen,
and heavy oil having an initial boiling point of more than 350 °C, wherein the "topped
crude oil" refers to an oil withdrawn from the bottom of a primary distillation column
or the bottom of a flash column during the fractionation of crude oil in an atmospheric
and vacuum distillation process.
[0034] According to the present application, the "deoiled asphalt" refers to the raffinate
rich in asphaltenes and aromatic components obtained at the bottom of an extraction
column, after contacting a feedstock oil with a solvent, dissolving and then separating
in a solvent deasphalting device, and can be classified into propane deoiled asphalt,
butane deoiled asphalt, pentane deoiled asphalt and the like according to the type
of the solvent.
[0035] According to the present application, the "coal derived oil" refers to a liquid fuel
obtained by subjecting coal to chemical processing as a raw material, and can be at
least one selected from coal liquefied oil obtained by coal liquefaction and coal
tar obtained by coal pyrolysis.
[0036] According to the present application, the "shale oil" refers to synthetic crude oil
obtained from oil shale by low-temperature dry distillation or other thermal treatment,
which may be a brown sticky paste and may have pungent odor and high nitrogen content.
[0037] According to the present application, the "petrochemical waste oil" may be at least
one selected from the group consisting of petrochemical waste oil sludge, petrochemical
oil residues, and refined products thereof.
[0038] According to the present application, the conversion product is subjected to a first
separation in step 2) to obtain a first separated product, wherein the content of
components having a boiling point below 350 °C in the first separated product is not
greater than about 5 wt%, preferably less than about 3 wt%, and the content of components
having a boiling point of 350-524 °C (preferably 355-500 °C or 380-524 °C, further
preferably 400-500 °C) is about 20-60 wt%, preferably about 25-55 wt%. Preferably,
the first separated product has an initial boiling point of no less than about 300
°C, preferably no less than about 330 °C, and more preferably no less than about 350
°C.
[0039] According to the present application, the first separated product generally consists
of components of the conversion product having a relatively higher boiling point,
which includes the pitch and the upgraded oil obtained in step 3), wherein the pitch
comprises asphaltenes as the main component, and some resin and aromatic components
necessary for maintaining fluidity; the upgraded oil can be used as a high-quality
raw material in subsequent process to produce other oil products. The remaining components
of the conversion product having a relatively lower boiling point may be separated
from the first separated product in step 2), such as gaseous products under standard
condition (e.g. dry gas and liquefied gas etc.) and other components having a boiling
point below 350 °C.
[0040] According to the present application, the first separation of step 2) is performed
to obtain a first separated product that meets the above-mentioned distillation range
configuration, and the present application has no specific requirement on the mode
for carrying out said separation. In certain embodiments, the first separation is
a physical separation, such as extraction, distillation, evaporation, flash evaporation,
condensation, or the like.
[0041] In a preferred embodiment, said first separation of step 2) comprises:
2a) separating the conversion product obtained in step 1) at a first pressure and
a first temperature to obtain a gas component and a liquid component; and
2b) separating the resulting liquid component at a second pressure and a second temperature
to yield the first separated product and a second separated product, wherein the first
pressure is greater than the second pressure.
[0042] According to the present application, it is preferable in step 2a) to separate out
gaseous products such as hydrogen, and the resulting gas component are enriched in
hydrogen, preferably with a hydrogen content of more than 85 wt%. Preferably, said
first pressure in step 2a), which for convenience of measurement generally refers
to the outlet pressure of the gas component exiting the separation device, may be
in a range of about 10-25 MPa, preferably about 13-20 MPa; the first temperature,
which for convenience of measurement generally refers to the outlet temperature of
the liquid component exiting the separation device, may be about 380-470 °C, preferably
about 400-440 °C. The separation mode of step 2a) may be selected from distillation,
fractionation, flash distillation and the like, preferably distillation. The distillation
may be carried out in a distillation column, wherein the gas component may be obtained
from the top of the distillation column and the liquid component may be obtained from
the bottom of the distillation column.
[0043] According to the present application, it is preferable in step 2b) to separate out
components having a boiling point below 350 °C while retaining as much as possible
components having a boiling point of 350-524 °C. Preferably, said second pressure
of step 2b) is lower than said first pressure, preferably 4-24 MPa, more preferably
7-19 MPa lower than said first pressure; in particular, the second pressure, which
for convenience of measurement generally refers to the outlet pressure of the second
separated product exiting the separation device, may be in a range of about 0.1-5
MPa, preferably 0.1-4 MPa; the second temperature, which for convenience of measurement
generally refers to the outlet temperature of the first separated product exiting
the separation device, can be about 150-390 °C, preferably 200-370 °C. The separation
mode of step 2b) may be distillation and/or fractionation, preferably atmospheric
or pressurized fractionation, and may be carried out in an atmospheric distillation
tank or a pressurized distillation column. According to the present application, the
second separated product obtained in step 2b) may comprise light components separated
out at the second pressure and second temperature that have a lower boiling point
than the first separated product.
[0044] In a further preferred embodiment, the first separation of step 2) may further comprise:
2c) splitting at least a part of the second separated product obtained in step 2b)
to obtain a naphtha and an atmospheric gas oil;
2d) recycling at least a part of the gas component obtained in step 2a) to step 1)
for conversion reaction; and/or
2e) recycling at least a part of the gas component obtained in step 2a) to step 4)
for the hydro-upgrading.
[0045] According to the present application, the splitting in step 2c) may be carried out
by fractionation or distillation, preferably by fractionation, for example in a fractionation
column, which may be operated at a pressure of 0.05-2.0 MPa, preferably about 0.1-1.0
MPa, and a temperature of 50-350 °C, preferably 150-330 °C.
[0046] According to the present application, in step 2d) and step 2e), at least a part of
the gas component obtained in step 2a) are recycled to step 1) and/or step 4), which
can be used directly or used after separation as recycled hydrogen.
[0047] In a still further preferred embodiment, the first separation of step 2) may further
comprise:
2f) recycling at least a part of the second separated product obtained in step 2b)
and/or at least a part of the atmospheric gas oil obtained in step 2c) to step 4)
for hydro-upgrading together with the upgraded oil.
[0048] According to the present application, said second separation of step 3) is used to
separate the upgraded oil, which is easy to process, from the pitch in the first separated
product, which is discarded or recycled to step 1) in step 7) for conversion reaction.
In some particular embodiments, the second separation of step 3) may be performed
at a third temperature and a third pressure using one or more of vacuum distillation
and solvent extraction. Specifically, the vacuum distillation may be carried out in
a distillation column with or without packing materials, wherein the third pressure
is a vacuum degree of about 1-20 mmHg and the third temperature is about 250 °C to
350 °C. The solvent extraction is preferably a countercurrent extraction of the first
separated product with an extraction solvent, which may be carried out in any extraction
apparatus, for example, in an extraction column, in which case the third pressure
may be about 3 to 12 MPa, preferably about 3.5 to 10 MPa, the third temperature may
be about 55 to 300 °C, preferably about 70 to 220 °C, the extraction solvent may be
C
3 to C
7 hydrocarbons, preferably at least one of C
3 to C
5 alkanes and C
3 to C
5 olefins, more preferably at least one of C
3 to C
4 alkanes and C
3 to C
4 olefins, and the weight ratio of the extraction solvent to the first separated product
is about 1:1 to about 7:1, preferably about 1.5:1 to about 5: 1. Other conventional
extraction methods may also be adopted, of which the detailed description is omitted
herein for brevity.
[0049] According to the present application, the pitch obtained in step 3) is the component
of the conversion product having the highest boiling point, the higher its softening
point the more completely those easily processable components of the conversion product
are separated, but in order to maintain the fluidity of the pitch during transport
through pipelines and the solubility of the pitch when recycling to the conversion
reactor, the softening point of the pitch obtained in step 3) is preferably less than
about 150 °C, more preferably less than about 120 °C.
[0050] According to the present application, when the conversion reaction is carried out
in a slurry bed reactor, the conversion catalyst in the slurry bed reactor will be
passed to subsequent separation steps along with the conversion product and remained
in the pitch, and the metal content in the whole reaction system will be increased
along with the increase of the amount of the catalyst added and the accumulation of
the metal component in the inferior oil. In order to maintain the balance of the metals
in the system, it is necessary to discharge the pitch intermittently or continuously,
preferably discard a part of the pitch, the proportion of the discarded pitch relative
to the total amount of the pitch is preferably about 5-70 wt%, more preferably about
10-50 wt%; also in order to make a full use of the inferior oil, it is preferable
to recycle a part of the pitch to step 1) in step 7), the proportion of the pitch
recycled is preferably about 30-95 wt%, more preferably about 50-90 wt%. The ratio
of the discarded pitch to the recycled pitch can be adjusted by the person skilled
in the art according to the metal contents of the inferior oil, of which the detailed
description is omitted herein for brevity.
[0051] According to the present application, in order to facilitate the production of the
chemical raw material, namely light olefins, the upgraded oil obtained is subjected
to hydro-upgrading in the step 4), the hydro-upgraded oil obtained is split into hydro-upgraded
light oil and hydro-upgraded heavy oil in the step 5), and the split point between
the hydro-upgraded light oil and the hydro-upgraded heavy oil can be about 340-360
°C, preferably about 345-355 °C and more preferably about 350 °C; and the hydro-upgraded
heavy oil obtained is subjected to catalytic cracking in the step 6) to obtain a catalytic
cracking product containing a light olefin. The catalytic cracking product can be
separated to obtain dry gas, light olefin, gasoline, cycle oil and slurry oil. The
"cycle oil" generally comprises light cycle oil and heavy cycle oil, wherein the light
cycle oil, which may also be referred to as diesel oil, refers to a fraction having
a boiling point between 205 °C and 350 °C obtained by catalytic cracking reaction,
and the heavy cycle oil refers to a fraction having a boiling point between 343 °C
and 500 °C; the "slurry oil" generally refers to the stream withdrawn from the bottom
of the settler in which the bottom oil obtained from the fractionation of catalytic
cracking product is separated, and the stream withdrawn from the top of the settler
is generally referred to as clarified oil.
[0052] Optionally, the slurry oil obtained can be recycled to the step 1) for conversion
reaction; the C3 and C4 hydrocarbons obtained are subjected to alkane-olefin separation,
and the C3 and C4 alkanes obtained are sent to the step 3) for use as an extraction
solvent; and/or, the cycle oil obtained is subjected to hydro-upgrading separately
or together with the upgraded oil. In the process of the present application, recycling
of the slurry oil for conversion reaction can be realized, so that, on one hand, the
utilization rate of the feedstock can be improved, and the slurry oil with low added
value can be converted into a gasoline product rich in aromatics with high added value;
on the other hand, the stability of the conversion unit can be improved, and the operation
period of the device can be prolonged, since the slurry oil is rich in aromatic components.
Meanwhile, at least a part of the second separated product obtained in step 2b) and/or
the atmospheric gas oil obtained in step 2c) can be catalytically cracked together
with the hydro-upgraded heavy oil in the step 6). By step 6) and the above-described
steps, maximized production of chemical raw materials from inferior oils can be realized
and the utilization rate of the upgraded oil and the second separated product can
be improved.
[0053] According to the present application, said hydro-upgrading involved in step 4) may
be that well known to the person skilled in the art and can be carried out in any
way known in the art, without any particular limitation, in any hydrotreating unit
known in the art (such as fixed bed reactor, fluidized bed reactor), which can be
reasonably selected by the person skilled in the art. For example, the hydro-upgrading
may be carried out under conditions including: a hydrogen partial pressure of about
5.0-20.0 MPa, preferably about 8-15 MPa; a reaction temperature between about 330
°C and 450 °C, preferably between about 350 °C and 420 °C; a volume space velocity
of about 0.1-3 h
-1, preferably about 0.3-1.5 h
-1; a hydrogen-to-oil volume ratio between about 300 and 3000, preferably between about
800 and 1500; a catalyst used for the hydro-upgrading including a hydrorefining catalyst
and/or a hydrocracking catalyst. The hydrorefining catalyst and the hydrocracking
catalyst may be any catalysts conventionally used in the art for this purpose, or
may be produced by any method conventionally known in the art, and the amounts of
the hydrorefining catalyst and the hydrocracking catalyst used in the step may be
determined in accordance with conventional knowledge in the art, without any particular
limitation.
[0054] For instance, the hydrorefining catalyst may comprise a carrier and an active metal
component selected from a Group VIB metal and/or a Group VIII non-noble metal, particularly
a combination of nickel and tungsten, a combination of nickel, tungsten and cobalt,
a combination of nickel and molybdenum, or a combination of cobalt and molybdenum.
These active metal components may be used alone or in combination at any ratio. Examples
of the carrier include alumina, silica, and amorphous silica-alumina. These carriers
may be used alone or in combination at any ratio. Preferably, the hydrorefining catalyst
may comprise about 30-80 wt% of an alumina carrier, about 5-40 wt% of molybdenum oxide,
about 5-15 wt% of cobalt oxide and about 5-15 wt% of nickel oxide, based on the dry
weight of the hydrorefining catalyst. Hydrorefining catalysts having other compositions
may also be employed by those skilled in the art.
[0055] The hydrocracking catalyst normally comprises a carrier, an active metal component
and a cracking active component. More specifically, examples of the active metal component
include sulfides of Group VIB metals, sulfides of Group VIII base metals, Group VIII
noble metals, and the like, and particularly, Mo sulfides, W sulfides, Ni sulfides,
Co sulfides, Fe sulfides, Cr sulfides, Pt, Pd, and the like. These active metal components
may be used alone or in combination at any ratio. Examples of the cracking active
component include amorphous silica-alumina, molecular sieves and the like. These cracking
active components may be used alone or in combination at any ratio. Examples of the
carrier include alumina, silica, titania, activated carbon and the like. These carriers
may be used alone or in combination at any ratio. The contents of the carrier, the
active metal component and the cracking active component are not particularly limited
in the present application and may be selected in accordance with conventional knowledge
in the art. Preferably, the hydrocracking catalyst may comprise about 3-60 wt% of
zeolite, about 10-80 wt% of alumina, about 1-15 wt% of nickel oxide and about 5-40
wt% of tungsten oxide, based on the dry weight of the hydrocracking catalyst, wherein
the zeolite is a Y zeolite. Hydrocracking catalysts having other compositions may
also be employed by those skilled in the art.
[0056] In a preferred embodiment, the catalyst used for the hydro-upgrading comprises both
a hydrofining catalyst and a hydrocracking catalyst, the loading volume ratio of the
hydrofining catalyst to the hydrocracking catalyst is about 1:1 to about 5:1, and
the hydrofining catalyst is loaded on the upstream of the hydrocracking catalyst along
the flow direction of the reaction materials.
[0057] According to the present application, the catalytic cracking of step 6) may be carried
out in various forms of catalytic cracking reactors, preferably in a varied-diameter
dilute-phase transport bed reactor and/or a combined catalytic cracking reactor.
[0058] In a preferred embodiment, the catalytic cracking of step 6) is carried out in a
varied-diameter dilute-phase transport bed reactor, wherein the varied-diameter dilute-phase
transport bed reactor comprises, from bottom to top, a first reaction zone and a second
reaction zone having different diameters, the ratio of the diameter of the second
reaction zone to the diameter of the first reaction zone being from about 1.2:1 to
about 2.0: 1. Preferably, in the varied-diameter dilute-phase transport bed reactor,
the reaction conditions in the first reaction zone may include: a reaction temperature
of about 500-620 °C, a reaction pressure of about 0.2-1.2MPa, a reaction time of about
0.1-5.0 seconds, a weight ratio of catalyst to cracking feedstock of about 5-15, and
a weight ratio of steam to cracking feedstock of about 0.05:1 to about 0.3: 1; the
reaction conditions in the second reaction zone may include: a reaction temperature
of about 450-550 °C, a reaction pressure of about 0.2-1.2MPa, and a reaction time
of about 1.0-20.0 seconds.
[0059] In another preferred embodiment, the catalytic cracking of step 6) is performed in
a combined catalytic cracking reactor, wherein the combined reactor has a first reaction
zone and a second reaction zone connected in series from bottom to top, the first
reaction zone is a riser reactor, the second reaction zone is a fluidized bed reactor,
and the fluidized bed reactor is located downstream of the riser reactor and connected
with an outlet of the riser reactor, for example, it can be a combined reactor obtained
by connecting a conventional catalytic cracking riser reactor and a fluidized bed
reactor in series, which are well known to those skilled in the art. In particular,
the riser reactor may be selected from an equal diameter riser reactor and/or an equal
linear velocity riser reactor, preferably an equal diameter riser reactor. The riser
reactor sequentially comprises a pre-lift section and at least one reaction zone from
bottom to top, and in order to enable feedstock oil to fully react and meet the quality
requirements of different target products, the number of the reaction zones can be
2-8, and preferably 2-3. Preferably, in the combined catalytic cracking reactor, the
reaction conditions in the first reaction zone may include: a reaction temperature
between about 560 °C and 750 °C, preferably between about 580 °C and 730 °C, and more
preferably between about 600 °C and 700 °C; a reaction time of about 1-10 seconds,
preferably about 2-5 seconds; a catalyst-to-oil ratio of about 1:1 to about 50:1,
preferably about 5:1 to about 30: 1; the reaction conditions in the second reaction
zone may include: a reaction temperature of about 550-730 °C, preferably about 570-720
°C; a weight space velocity of about 0.5-20 h
-1, preferably about 2-10 h
-1 .
[0060] In a further preferred embodiment, steam may be injected into the riser reactor,
preferably in the form of atomizing steam, and the weight ratio of injected steam
to feedstock oil may be from about 0.01:1 to about 1:1, preferably from about 0.05:1
to about 0.5: 1.
[0061] In some embodiments, the process of the present application may further comprise
separating the spent catalyst from the reaction oil gas in the catalytic cracking
product to obtain the spent catalyst and the reaction oil gas, separating the reaction
oil gas obtained into fractions such as dry gas, liquefied gas, gasoline and diesel
oil in a subsequent separation system, and further separating the dry gas and the
liquefied gas in a gas separation device to obtain ethylene, propylene, and the like.
The method for separating ethylene, propylene, and the like from the reaction product
may adopt conventional technique in the art, and is not particularly limited in the
present application, of which the detailed description is omitted herein for brevity.
[0062] In certain embodiments, the process of the present application may further comprise
regenerating the spent catalyst; and preferably, at least a part of the catalyst used
for the catalytic cracking reaction is regenerated catalyst, and for example, may
totally be regenerated catalyst.
[0063] In certain embodiments, the process of the present application may further comprise
stripping the regenerated catalyst, typically with steam, to remove impurities such
as gases.
[0064] According to the present application, during regeneration, an oxygen-containing gas,
which may be, for example, air, is generally introduced from the bottom of the regenerator.
After the catalyst is introduced into the regenerator, the spent catalyst is contacted
with oxygen for regeneration by coke-burning, the flue gas generated after the regeneration
of the catalyst is subjected to gas-solid separation at the upper part of the regenerator,
and then the flue gas is passed to a subsequent energy recovery system.
[0065] According to the present application, the regeneration conditions for the spent catalyst
may include: a regeneration temperature of about 550-750 °C, preferably about 600-730
°C, and more preferably about 650-700 °C; a superficial gas linear velocity of about
0.5-3 m/s, preferably about 0.8-2.5 m/s, more preferably about 1-2 m/s, and an average
residence time of the spent catalyst of about 0.6-3 minutes, preferably about 0.8-2.5
minutes, more preferably about 1-2 minutes.
[0066] According to the present application, the catalytic cracking catalyst suitable for
step 6) may be various catalytic cracking catalysts conventionally used in the art.
Preferably, the catalytic cracking catalyst may comprise, based on the total weight
of the catalyst, about 1-60 wt% of zeolite, about 5-99 wt% of inorganic oxide, and
about 0-70 wt% of clay.
[0067] According to the present application, in the catalytic cracking catalyst, the zeolite
is used as an active component, and preferably, the zeolite is selected from mesoporous
zeolite and/or macroporous zeolite. In a preferred embodiment, the mesoporous zeolite
is present in an amount of about 50-100 wt%, preferably about 70-100 wt%, and the
macroporous zeolite is present in an amount of about 0-50 wt%, preferably about 0-30
wt%, based on the total weight of the zeolite.
[0068] According to the present application, the mesoporous and macroporous zeolites have
the meaning generally understood in the art, in which the average pore size of the
mesoporous zeolite is 0.5-0.6 nm and the average pore size of the macroporous zeolite
is 0.7-1.0 nm. For example, the macroporous zeolite may be selected from the group
consisting of rare earth Y zeolite (REY), rare earth hydrogen Y zeolite (REHY), ultrastable
Y zeolite obtained by different methods, high silicon Y zeolite, and mixtures of two
or more thereof.
[0069] In a preferred embodiment, the mesoporous zeolite may be selected from zeolites having
a MFI structure, such as ZSM series zeolites and/or ZRP zeolites. Optionally, the
mesoporous zeolite may be modified with a nonmetallic element such as phosphorus and/or
a transition metal element such as iron, cobalt, and nickel. For a more detailed description
of ZRP zeolites, reference may be made to
U.S. patent No. 5,232,675, which is incorporated herein by reference in its entirety; the ZSM-series zeolite
may be selected from the group consisting of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35,
ZSM-38, ZSM-48, other zeolites having a similar structure, or mixtures of two or more
thereof. more detailed description of ZSM-5 may be found in
U.S. patent 3,702,886, which is incorporated herein by reference in its entirety.
[0070] According to the present application, in the catalytic cracking catalyst, the inorganic
oxide is used as a binder, and is preferably selected from silica (SiO
2) and/or alumina (Al
2O
3).
[0071] According to the present application, in the catalytic cracking catalyst, the clay
is used as a matrix (i.e. support), and is preferably selected from kaolin and/or
halloysite.
[0072] In a particularly preferred embodiment, the process of the present application comprises
the steps of:
- 1) subjecting an inferior oil feedstock to thermal conversion reaction in the presence
of hydrogen to obtain a conversion product, wherein the conversion rate of the conversion
reaction is about 30-70 wt%, and the conversion rate = (weight of components having
a boiling point above 524 °C in the inferior oil - weight of components having a boiling
point above 524 °C in the conversion product)/weight of components having a boiling
point above 524 °C in the inferior oil ×100 wt%;
- 2) subjecting the conversion product obtained in step 1) to a first separation to
obtain a first separated product, wherein the content of components having a boiling
point below 350 °C in the first separated product is not greater than about 5 wt%,
preferably less than about 3 wt%, the content of components having a boiling point
between 350 °C and 524 °C (preferably between 355 °C and 500 °C or between 380 °C
and 524 °C, further preferably between 400 °C and 500 °C) is about 20-60 wt%, preferably
about 25-55 wt%, and the initial boiling point of the first separated product is not
lower than about 300 °C, preferably not lower than about 330 °C, and more preferably
not lower than about 350 °C;
- 3) subjecting the first separated product obtained in step 2) to a second separation
to obtain an upgraded oil and a pitch, wherein the second separation is selected from
vacuum distillation, solvent extraction or a combination of vacuum distillation and
solvent extraction;
- 4) subjecting the upgraded oil obtained in step 3) to hydro-upgrading to obtain a
hydro-upgraded oil;
- 5) subjecting the hydro-upgraded oil obtained in step 4) to a third separation to
obtain a hydro-upgraded heavy oil;
- 6) preheating the hydro-upgraded heavy oil obtained in step 5), then feeding it into
the bottom of a varied-diameter dilute-phase transport bed reactor, contacting it
with a regenerated catalyst to perform catalytic cracking reaction, allowing the reaction
stream to flow upward and enter a cyclone separator to perform gas-solid separation,
and further separating the separated reaction oil gas to obtain a product containing
propylene and high-octane gasoline; stripping the separated spent catalyst and then
passing it to a catalyst regenerator for regeneration by coke-burning, and recycling
the regenerated catalyst to the reactor for reuse; or
alternatively, preheating the hydro-upgraded heavy oil obtained in step 5), then feeding
it into a first reaction zone of a combined catalytic cracking reactor, and contacting
it with a regenerated catalyst to perform catalytic cracking reaction, allowing the
reaction stream to flow upward and enter a second reaction zone for further catalytic
cracking reaction, passing the reaction oil gas and the spent catalyst at the outlet
of the reactor into a cyclone separator to perform gas-solid separation, and further
separating the separated reaction oil gas to obtain a product comprising a light olefin;
stripping the separated spent catalyst and passing it to a catalyst regenerator for
regeneration by coke-burning, and recycling the regenerated catalyst to the reactor
for reuse, wherein the light olefin includes ethylene, propylene and butylene; and
- 7) recycling the pitch obtained in step 3) to the step 1) for conversion reaction;
or, discarding the pitch obtained in step 3); or recycling a part of the pitch obtained
in step 3) to the step 1) for conversion reaction, and discarding the rest of the
pitch.
[0073] In a second aspect, the present application provides a system for producing light
olefins from inferior oils, including a conversion reaction unit, a first separation
unit, a second separation unit, a hydro-upgrading unit, a third separation unit and
a catalytic cracking unit, wherein:
the conversion reaction unit is configured to carry out a thermal conversion reaction
on an inferior oil feedstock in the presence of hydrogen to obtain a conversion product;
the first separation unit is configured to separate the conversion product to obtain
a first separated product, wherein in the first separated product, the content of
components having a boiling point below 350 °C is not greater than about 5 wt%, and
the content of components having a boiling point between 350 °C and 524 °C is about
20-60 wt%;
the second separation unit is configured to separate the first separated product into
an upgraded oil and a pitch, and is selected from a vacuum distillation unit, a solvent
extraction unit or a combination thereof;
the hydro-upgrading unit is configured to carry out hydro-upgrading reaction on the
upgraded oil to obtain a hydro-upgraded oil;
the third separation unit is configured to separate the hydro-upgraded oil to obtain
a hydro-upgraded heavy oil; and
the catalytic cracking unit is configured to carry out catalytic cracking reaction
on the hydro-upgraded heavy oil to obtain a catalytic cracking product comprising
a light olefin.
[0074] According to certain embodiments of the present application, in the conversion reaction
unit, the inferior oil, hydrogen and conversion catalyst are reacted in the conversion
reactor to obtain a conversion product, which is then sent to the first separation
unit. Preferably, the conversion reactor is a slurry bed reactor.
[0075] According to certain embodiments of the present application, in the first separation
unit, the conversion product is first separated into a gaseous product and a liquid
product, and then the liquid product is further separated to obtain a heavy fraction
having a distillation range greater than about 350 °C as the first separated product,
which is then sent to a second separation unit.
[0076] According to certain embodiments of the present application, in the second separation
unit, the first separated product is separated in a vacuum distillation column, or
is subjected to extractive separation in an extraction column by countercurrently
contacting with an extraction solvent to obtain the upgraded oil and the pitch, or
is separated in a combination of vacuum distillation and extractive separation to
obtain the upgraded oil and the pitch, and the upgraded oil is sent to a hydro-upgrading
unit. Optionally, the pitch is recycled to the conversion reaction unit for further
conversion.
[0077] According to certain embodiments herein, in the hydro-upgrading unit, the upgraded
oil is reacted in the presence of a hydrotreating catalyst to obtain a hydro-upgraded
oil, which is then sent to a third separation unit.
[0078] According to certain embodiments of the present application, in the third separation
unit, the hydro-upgraded oil is split into a hydro-upgraded light oil and a hydro-upgraded
heavy oil, and the hydro-upgraded heavy oil is sent to a catalytic cracking unit.
[0079] According to certain embodiments of the present application, the catalytic cracking
unit comprises a varied-diameter dilute-phase transport bed reactor and/or a combined
catalytic cracking reactor, wherein the varied-diameter dilute-phase transport bed
reactor comprises, from bottom to top, a first reaction zone and a second reaction
zone having different diameters, the ratio of the diameter of the second reaction
zone to the diameter of the first reaction zone is from about 1.2:1 to about 2.0:
1; the combined catalytic cracking reactor comprises a first reaction zone and a second
reaction zone from bottom to top, wherein the first reaction zone is a riser reactor,
and the second reaction zone is a fluidized bed reactor.
[0080] According to a preferred embodiment of the present application, in the catalytic
cracking unit, a catalytic cracking catalyst is fed to a pre-lift section of a first
reaction zone of a varied-diameter dilute-phase transport bed reactor, and flows upward
under the action of a pre-lifting medium, and the preheated hydro-upgrading heavy
oil and atomizing steam are injected into the first reaction zone together, contacted
with a regenerated catalyst to perform a catalytic cracking reaction and flow upward
at the same time, and then enter a second reaction zone for further reaction to obtain
a catalytic cracking product comprising a light olefin. Optionally, the catalytic
cracking product is separated in a subsequent separation system to obtain fractions
such as ethylene, propylene and gasoline with a high octane number; the separated
spent catalyst is passed to a regenerator for regeneration by coke-burning, and the
regenerated catalyst with recovered activity is recycled to the varied-diameter dilute-phase
transport bed reactor for reuse.
[0081] According to another preferred embodiment of the present application, in the catalytic
cracking unit, the catalytic cracking catalyst is fed to a pre-lift section of a first
reaction zone of a combined catalytic cracking reactor, and flows upward under the
action of a pre-lifting medium, the preheated hydro-upgraded oil and atomizing steam
are injected into the first reaction zone together, contacted with a regenerated catalyst
to perform the catalytic cracking reaction and flow upward at the same time, and then
enter a second reaction zone for further reaction to obtain a catalytic cracking product
containing a light olefin. Optionally, the catalytic cracking product is separated
in a subsequent separation system to obtain fractions such as ethylene, propylene,
and cracking gasoline; the separated spent catalyst is passed to a regenerator for
regeneration by coke-burning, and the regenerated catalyst with recovered activity
is recycled to the combined catalytic cracking reactor for reuse.
[0082] The following detailed description of embodiments of the present application is provided
with reference to the accompanying drawings.
[0083] As shown in Figs. 1a, 1b, 2a and 2b, an inferior feedstock is transferred via pipeline
1, a conversion catalyst is transferred via pipeline 2, a fresh hydrogen is transferred
via pipeline 3, a recycle hydrogen is transferred via pipeline 4, a catalytic slurry
is transferred via pipeline 57 and a pitch is transferred via pipeline 5 to a conversion
reactor 6 for thermal conversion reaction. The conversion product is sent to a high
pressure separation unit 8 for pressure distillation via pipeline 7, and is separated
into a gas component and a liquid component, and then the gas component is sent to
the conversion reactor 6 via pipeline 9 and pipeline 4 as recycle hydrogen or sent
to a hydro-upgrading unit 23 via pipeline 9 and pipeline 11 as hydrogen source. The
liquid component is sent via pipeline 10 to a low pressure separation unit 12 and
separated into a second separated product and a first separated product by abrupt
pressure drop. The second separated product is passed to a hydro-upgrading unit 23
through pipeline 14, the first separated product is passed to a second separating
unit 17 through pipeline 15 for vacuum distillation to obtain an upgraded oil and
a pitch (see Figs. 1a and 2a), or the first separated product is countercurrently
contacted with an extraction solvent from pipeline 16 and/or pipeline 55 for extractive
separation in a second separating unit 17 to obtain an upgraded oil and a pitch (see
Figs. 1b and 2b). A part of the pitch is discarded through pipeline 19 and pipeline
20, and the rest is recycled to the conversion reactor 6 through pipeline 19 and pipeline
5 for further reaction together with the inferior oil feedstock. Alternatively, all
of the pitch may be discarded via pipelines 19 and 20 without being recycled. The
upgraded oil withdrawn through pipeline 18 is mixed with the second separated product
from pipeline 14 and the catalytic diesel oil from pipeline 21, and is fed to the
hydro-upgrading unit 23 through pipeline 22 for hydro-upgrading, the resulting hydro-upgraded
product is separated, the resulting light components and hydro-upgraded light oil
are respectively withdrawn through pipeline 24 and pipeline 25, or the hydro-upgraded
light oil withdrawn through pipeline 25 is mixed with the hydro-upgraded heavy oil
withdrawn through pipeline 26 and is sent to a first reaction zone 29 of a catalytic
cracking unit (i.e. the varied-diameter dilute-phase transport bed reactor shown in
Fig. 1a and 1b, or the combined catalytic cracking reactor shown in Fig. 2a and 2b)
through pipeline 28. Meanwhile, the pre-lifting medium is also fed to the first reaction
zone 29 through pipeline 50. The regenerated catalyst from pipeline 48 is fed to the
first reaction zone 29 after being regulated by the regenerated catalyst slide valve
49, and flows upward along the riser under the action of the pre-lifting medium, the
preheated hydro-upgraded oil is injected into the first reaction zone 29 through pipeline
28 together with the atomizing steam from pipeline 27, and is mixed with the stream
in the first reaction zone 29. The feedstock oil undergoes a catalytic cracking reaction
on the hot catalyst and flows upward, and then enters the second reaction zone 30
of the catalytic cracking unit for further reaction. The generated oil gas product
and inactivated spent catalyst are passed to a cyclone separator 34 in a disengager
33 to perform the separation of the spent catalyst and the oil gas product, the oil
gas product is passed to a gas collection chamber 35, and fine catalyst powders are
returned to the disengager. Spent catalyst in the disengager flows to the stripping
section 32 where it contacts steam from pipeline 31. The oil gas product stripped
out from the spent catalyst is passed to the gas collection chamber 35 after passing
through the cyclone separator. The stripped spent catalyst is passed to a regenerator
39 after being regulated by a spent catalyst slide valve 38, and air from pipeline
44 is fed to the regenerator 39 after being distributed by an air distributor 43.
Coke on the spent catalyst is burnt out in a dense bed at the bottom of the regenerator
39, so as to regenerate the deactivated spent catalyst, and flue gas is passed to
a subsequent energy recovery system through flue gas pipeline 41 at an upper part
of a cyclone separator 40. The pre-lifting medium can be dry gas, steam or a mixture
thereof.
[0084] The regenerated catalyst is fed to a degassing tank 46 through pipeline 45 communicated
with a catalyst outlet of the regenerator 39, and is contacted with a stripping medium
from pipeline 47 at the bottom of the degassing tank 46 to remove flue gas entrained
by the regenerated catalyst. The degassed regenerated catalyst is recycled to the
bottom of the first reaction zone 29 through pipeline 48, of which the circulation
amount can be controlled by the regenerated catalyst slide valve 49. The gas is returned
to the regenerator 39 through pipeline 42, the oil gas product in the gas collection
chamber 35 is passed to a subsequent separation system 58 through vapor line 36, H
2 and C1-C2 alkane obtained through separation are withdrawn through pipeline 53, and
the light olefin (including C2, C3 and C4 olefins) obtained is sent out of the system
through pipeline 54; C3 and C4 alkanes are sent out of the system through pipeline
55 or sent into the second separation unit 17 for use as an extraction solvent, the
gasoline obtained rich in aromatics is withdrawn through pipeline 56 as a product,
the cycle oil obtained is withdrawn through pipeline 21 and is mixed with the upgraded
oil from pipeline 18 and the second separated product from pipeline 14, and then sent
to the hydro-upgrading unit 23 for hydro-upgrading, and the slurry oil obtained is
withdrawn through pipeline 57 and recycled to the conversion reactor 6 for thermal
conversion reaction.
[0085] Optionally, as shown in Figs. 1a and 1b, C4 or light gasoline fraction separated
from the catalytic cracking product can be recycled to a second reaction zone 30 of
the varied-diameter dilute-phase transport bed reactor acting as the catalytic cracking
unit through pipeline 52 and pipeline 51 together with steam for further cracking
to increase the yield of light olefins.
[0086] In certain preferred embodiments, the present application provides the following
technical solutions:
A1. a process for producing light olefins from inferior oils, comprising the steps
of:
- (1) feeding an inferior oil to a conversion reaction unit for conversion reaction,
and separating the resulting reaction product to obtain a heavy fraction having a
boiling point above about 350 °C;
- (2) sending the heavy fraction into a vacuum distillation separation unit and/or an
extractive separation unit for separation to obtain an upgraded oil and a pitch;
- (3) feeding the upgraded oil into a hydro-upgrading unit for hydro-upgrading to obtain
a hydro-upgraded oil;
- (4) feeding the hydro-upgraded oil after preheating to a first reaction zone of a
catalytic cracking reactor, contacting it with a regenerated catalyst to perform catalytic
cracking reaction, allowing the reaction stream to flow upward and enter a second
reaction zone for further catalytic cracking reaction, passing the resulting oil gas
and spent catalyst at the outlet of the reactor to a cyclone separator for gas-solid
separation, withdrawing the separated oil gas from the device, and further separating
it to obtain a product containing a light olefin; stripping the separated spent catalyst
and passing it to a catalyst regenerator for regeneration by coke-burning, and recycling
the regenerated catalyst to the reactor for reuse.
A2. the process according to Item A1, wherein the inferior oil comprising at least
one selected from the group consisting of inferior crude oil, heavy oil, deoiled asphalt,
coal derived oil, shale oil, and petrochemical waste oil.
A3. the process according to Item A1, wherein the feedstock to be upgraded satisfies
one or more the following criteria: an API degree of less than about 27, a distillation
range of greater than about 350 °C, an asphaltene content of greater than about 2
wt%, and a heavy metal content of greater than about 100 µg/g calculated as the total
weight of nickel and vanadium.
A4. the process according to Item A1, wherein the conversion reactor of the conversion
reaction unit is a fluidized bed reactor.
A5. the process according to Item A1, wherein the conversion catalyst of the conversion
reaction unit comprises at least one compound selected from the group consisting of
Group VB metal compounds, Group VIB metal compounds, and Group VIII metal compounds.
A6. the process according to Item A1, wherein the reaction conditions of the conversion
reaction unit include: a temperature of about 380-470 °C, a hydrogen partial pressure
of 10-25 MPa, a volume space velocity of the inferior oil of about 0.01-2 h-1, a volume ratio of hydrogen to the inferior oil of about 500-5000, and an amount
of the conversion catalyst of about 10-50000 µg/g calculated on the basis of the metal
in the conversion catalyst and relative to the weight of the inferior oil.
A7. the process according to Item A1, wherein the operating conditions of the extractive
separation unit include: a pressure of about 3-12 MPa, a temperature of about 55-300
°C, an extraction solvent of C3-C7 hydrocarbons, and a weight ratio of solvent to heavy fraction of (1-7): 1, or
the operating conditions of the vacuum distillation separation unit include: a vacuum
degree of about 1-20 mmHg and a temperature of about 250-350 °C.
A8. the process according to Item A1, wherein the reaction conditions for hydro-upgrading
unit include: a hydrogen partial pressure of about 5.0-20.0 MPa, a reaction temperature
of about 330-450 °C, a volume space velocity of about 0.1-3 h-1, and a hydrogen-to-oil volume ratio of about 300-3000.
A9. the process according to Item A1, wherein the catalyst used in the hydro-upgrading
unit comprises a hydrorefining catalyst and a hydrocracking catalyst, the hydrorefining
catalyst comprises a carrier and an active metal component, and the active metal component
is selected from Group VIB metals and/or Group VIII non-noble metals; the hydrocracking
catalyst comprises a zeolite, alumina, at least one Group VIII metal component and
at least one Group VIB metal component.
A10. the process according to Item A1, wherein, based on the weight of the catalyst,
the hydrocracking catalyst comprises: 3-60 wt% of zeolite, 10-80 wt% of alumina, 1-15
wt% of nickel oxide and 5-40 wt% of tungsten oxide.
A11. the process according to Item A1, wherein the reactor of the catalytic cracking
unit comprises a first reaction zone and a second reaction zone, the first reaction
zone is a riser reactor, and the second reaction zone is a fluidized bed reactor.
A12. the process according to Item A1, wherein the conditions in the first reaction
zone include: a reaction temperature of 560-750 °C, a reaction time of 1-10 seconds,
and a catalyst-to-oil ratio of 1-50: 1; the conditions in the second reaction zone
include: a reaction temperature of 550-700 °C, and a space velocity of about 0.5-20
h-1 .
A13. the process according to Item A1, wherein the catalyst used in step (4) comprises:
1-60 wt% of zeolite, 5-99 wt% of inorganic oxide and 0-70 wt% of clay, based on the
total weight of the catalyst, wherein the zeolite is selected from mesoporous zeolite
and optional macroporous zeolite, the mesoporous zeolite accounts for 50-100 wt% of
the total weight of the zeolite, and the macroporous zeolite accounts for 0-50 wt%
of the total weight of the zeolite.
A14. the process according to Item A13, wherein the mesoporous zeolite accounts for
70-100 wt% of the total weight of the zeolite, and the macroporous zeolite accounts
for 0-30 wt% of the total weight of the zeolite.
A15. the process according to Item A1, wherein the pitch of step (2) is recycled to
step (1) for conversion reaction; or, the pitch obtained in step (2) is discarded;
or a part of the pitch obtained in step (2) is recycled to step (1) for conversion
reaction, and the rest of the pitch is discarded.
A16. the process according to Item A1, wherein the conversion rate of the conversion
reaction is about 30-70 wt%, the conversion rate of the conversion reaction = (weight
of components having a distillation range above 524 °C in the inferior oil - weight
of components having a distillation range above 524 °C in the conversion product)/weight
of components having a distillation range above 524 °C in the inferior oil ×100 wt%;
and/or the content of components having a distillation range between 350 °C and 524
°C in the heavy fraction is about 20-60 wt%.
A17. a system for producing light olefins from inferior oils, comprising a conversion
reaction unit, an extractive separation or vacuum distillation separation unit, a
hydro-upgrading unit and a catalytic cracking unit, wherein the conversion reaction
unit is connected to the vacuum distillation and/or extractive separation unit, the
vacuum distillation and/or extractive separation unit is connected to the hydro-upgrading
unit, and the hydro-upgrading unit is connected to the catalytic cracking unit.
B1. an upgrading process for producing light olefins from inferior oils, comprising
the steps of:
- (1) subjecting an inferior oil serving as the feedstock to be upgraded to conversion
reaction in the presence of hydrogen to obtain a conversion product; wherein the conversion
rate of the conversion reaction is about 30-70 wt%, the conversion rate of the conversion
reaction = (weight of components having a boiling point above 524 °C in the feedstock
to be upgraded - weight of components having a boiling point above 524 °C in the conversion
product)/weight of components having a boiling point above 524 °C in the feedstock
to be upgraded ×100 wt%;
- (2) separating the conversion product obtained in step (1) to obtain at least a first
separated product; wherein in the first separated product, the content of components
having a boiling point below 350 °C is not greater than about 5 wt%, and the content
of components having a boiling point between 350 °C and 524 °C is about 20-60 wt%;
- (3) separating the first separated product obtained in step (2) in a vacuum distillation
separation unit via vacuum distillation and/or in an extractive separation unit via
extractive separation using an extraction solvent, to obtain an upgraded oil and a
pitch;
- (4) recycling the pitch obtained in step (3) to step (1) for conversion reaction;
or, discarding the pitch obtained in step (3); or, recycling a part of the pitch obtained
in step (3) to step (1) for conversion reaction, and discarding the rest of the pitch;
- (5) subjecting the upgraded oil obtained in step (3) to hydro-upgrading to obtain
a hydro-upgraded oil;
- (6) separating the hydro-upgraded oil obtained in step (5), and subjecting the resulting
hydro-upgraded heavy oil to catalytic conversion reaction to obtain a product containing
a light olefin.
B2. the upgrading process according to Item B1, wherein in step (1), the conversion
rate of the conversion reaction is about 30-60 wt%.
B3. the upgrading process according to Item B1, wherein in step (1), the conversion
reaction is carried out in a slurry bed reactor.
B4. the upgrading process according to Item B1, wherein in step (1), the conversion
reaction is carried out in the presence or absence of a conversion catalyst comprising
at least one selected from the group consisting of Group VB metal compounds, Group
VIB metal compounds, and Group VIII metal compounds.
B5. the upgrading process according to Item B1, wherein in step (1), the conversion
reaction conditions include: a temperature of about 380-470 °C, a hydrogen partial
pressure of 10-25 MPa, a volume space velocity of the feedstock to be upgraded of
about 0.01-2 h-1, a volume ratio of hydrogen to the feedstock to be upgraded of about 500-5000, and
an amount of the conversion catalyst of about 10-50000 µg/g calculated on the basis
of the metal in the hydrogen conversion catalyst and relative to the weight of the
feedstock to be upgraded.
B6. the upgrading process according to Item B1, wherein in step (1), the feedstock
to be upgraded comprises at least one selected from the group consisting of inferior
crude oil, heavy oil, deoiled asphalt, coal derived oil, shale oil and petrochemical
waste oil.
B7. the upgrading process according to Item B1, wherein the feedstock to be upgraded
satisfies one or more of the following criteria: an API degree of less than about
27, a boiling point of greater than about 350 °C, an asphaltene content of greater
than about 2 wt%, and a heavy metal content of greater than about 100 µg/g calculated
as the total weight of nickel and vanadium.
B8. the upgrading process according to Item B1, wherein in step (2), in the first
separated product, the content of components having a boiling point below 350 °C is
less than about 3 wt%, and the content of components having a boiling point between
350 °C and 524 °C is about 25-55 wt%.
B9. the upgrading process according to Item B1, wherein in step (2), the separation
comprises:
(2-1) separating the conversion product obtained in step (1) at a first pressure and
a first temperature to obtain a gas component and a liquid component;
(2-2) separating the liquid component at a second pressure and a second temperature
to obtain the first separated product and a second separated product; wherein the
first pressure is greater than the second pressure.
B10. the upgrading process according to Item B9, wherein the first pressure is 10-25
MPa and the first temperature is about 380-470 °C; the second pressure is about 0.1-5
MPa and the second temperature is about 150-390°C.
B11. the upgrading process according to Item B9, wherein the separation further comprises:
(2-3) splitting the second separated product obtained in step (2-2) to obtain a naphtha
and an atmospheric gas oil; and/or
(2-4) recycling the gas component obtained in step (2-1) to step (1) for conversion
reaction and/or to step (5) for hydro-upgrading.
B12. the upgrading process according to Item B11, wherein the second separated product
and/or atmospheric gas oil is hydro-upgraded together with the upgraded oil.
B13. the upgrading process according to Item B1 or B12, wherein the conditions of
the hydro-upgrading of step (5) include: a hydrogen partial pressure of about 5.0-20.0
MPa, a reaction temperature of about 330-450 °C, a volume space velocity of about
0.1-3 h-1, and a hydrogen-to-oil volume ratio of about 300-3000.
B14. the upgrading process according to Item B1 or B12, wherein the catalyst used
in the hydro-upgrading of step (5) comprises a hydrorefining catalyst and a hydrocracking
catalyst, the hydrorefining catalyst comprises a carrier and an active metal component,
and the active metal component is selected from Group VIB metals and/or Group VIII
non-noble metals; the hydrocracking catalyst comprises a zeolite, alumina, at least
one Group VIII metal component and at least one Group VIB metal component.
B15. the upgrading process according to Item B14, wherein the hydrocracking catalyst
comprises about 3-60 wt% of zeolite, about 10-80 wt% of alumina, about 1-15 wt% of
nickel oxide and about 5-40 wt% of tungsten oxide based on the dry weight of the hydrocracking
catalyst.
B16. the upgrading process according to Item B1, wherein the catalytic conversion
reaction of step (6) is carried out in a catalytic conversion reactor in the presence
of a catalytic conversion catalyst, wherein the catalytic conversion reactor is selected
from the group consisting of riser reactor, fluidized bed reactor, down-flow conveying
reactor, moving bed reactor, or a composite reactor combining any two thereof.
B17. the upgrading process according to Item B1, wherein the conditions of the catalytic
conversion reaction of step (6) include: a reaction temperature of 500-750 °C, the
reaction pressure of 0.15-0.50 MPa, a reaction time of 0.2-10 seconds, a catalyst-to-oil
ratio of 5-40, and a water-to-oil ratio of 0.05-1.0.
B18. the upgrading process according to Item B1, wherein the catalytic conversion
catalyst of step (6) comprises a zeolite, an inorganic oxide, and optionally a clay,
in amounts of: 1-60 wt% of zeolite, 5-99 wt% of inorganic oxide and 0-70 wt% of clay,
wherein the zeolite is a mixture of mesoporous zeolite and optional macroporous zeolite,
the proportion of the mesoporous zeolite is 50-100 wt%, preferably 70-100 wt%, and
the proportion of the macroporous zeolite is 0-50 wt%, preferably 0-30 wt%.
B19. the upgrading process according to Item B1, wherein in step (3), the extractive
separation is conducted using an extraction solvent at a third temperature and a third
pressure; wherein the third pressure is about 3-12 MPa, the third temperature is about
55-300 °C, the extraction solvent is C3-C7 hydrocarbon, and the weight ratio of extraction solvent to first separated product
is (1-7): 1.
B20. the upgrading process according to Item B1, wherein in step (3), the pitch has
a softening point of less than about 150 °C.
B21. the upgrading process according to Item B1, wherein in step (4), the proportion
of the pitch recycled to step (1) to the total amount of the pitch is 30-95 wt%, preferably
50-90 wt%.
B22. the upgrading process according to Item B1, wherein in step (6), the hydro-upgraded
oil is split into hydro-upgraded light oil and hydro-upgraded heavy oil, and the split
point between the hydro-upgraded light oil and the hydro-upgraded heavy oil is 340-360
°C, preferably about 345-355 °C and more preferably about 350 °C.
B23. an upgrading system for producing light olefins produced from inferior oil, comprising
a hydro-conversion reaction unit, a vacuum distillation and/or an extractive separation
unit, a hydro-upgrading unit and a catalytic conversion unit, wherein the hydro-conversion
reaction unit is connected to the vacuum distillation and/or extractive separation
unit, the vacuum distillation and/or extractive separation unit is connected to the
hydro-upgrading unit, and the hydro-upgrading unit is connected to the catalytic conversion
unit.
C1. a process for producing propylene and high-octane gasoline from inferior oils,
comprising the steps of:
- (1) feeding an inferior oil to a conversion reaction unit for conversion reaction,
and separating the resulting reaction product to obtain a heavy fraction having a
distillation range above about 350 °C;
- (2) sending the heavy fraction to a vacuum distillation separation unit and/or an
extractive separation unit for separation to obtain an upgraded oil and a pitch;
- (3) feeding the upgraded oil into a hydro-upgrading unit for hydro-upgrading to obtain
a hydro-upgraded oil;
- (4) feeding the hydro-upgraded oil after preheating to the bottom of a varied-diameter
dilute-phase transport bed reactor, contacting it with a regenerated catalyst to perform
catalytic cracking reaction, allowing the reaction stream to flow upward and enter
a cyclone separator for gas-solid separation, withdrawing the separated reaction oil
gas from the device and further separating it to obtain a product containing propylene
and high-octane gasoline; stripping the separated spent catalyst and passing it to
a catalyst regenerator for regeneration by coke-burning, and recycling the regenerated
catalyst to the reactor for reuse.
C2. the process according to Item C1, wherein the inferior oil comprises at least
one selected from the group consisting of inferior crude oil, heavy oil, deoiled asphalt,
coal derived oil, shale oil, and petrochemical waste oil.
C3. the process according to Item C1, wherein the feedstock to be upgraded satisfies
one or more of the following criteria: an API degree of less than about 27, a distillation
range of greater than about 350 °C, an asphaltene content of greater than about 2
wt%, and a heavy metal content of greater than about 100 µg/g, calculated as the total
weight of nickel and vanadium.
C4. the process according to Item C1, wherein the conversion reactor of the conversion
reaction unit is a slurry bed reactor.
C5. the process according to Item C1, wherein the conversion catalyst of the conversion
reaction unit comprises at least one selected from the group consisting of Group VB
metal compounds, Group VIB metal compounds and Group VIII metal compounds.
C6. the process according to Item C1, wherein the reaction conditions of the conversion
reaction unit include: a temperature of about 380-470 °C, a hydrogen partial pressure
of 10-25 MPa, a volume space velocity of the inferior oil of about 0.01-2 h-1, a volume ratio of hydrogen to the inferior oil of about 500-5000, and an amount
of the conversion catalyst of about 10-50000 µg/g calculated on the basis of the metal
in the conversion catalyst and relative to the weight of the feedstock to be upgraded.
C7. the process according to Item C1, wherein the reaction conditions of the extractive
separation unit include: a pressure of about 3-12 MPa, a temperature of about 55-300
°C, an extraction solvent of C3-C7 hydrocarbon, a weight ratio of solvent to heavy fraction of (1-7): 1, or
the operating conditions of the vacuum distillation separation unit include: a vacuum
degree of about 1-20 mmHg and a temperature of about 250-350 °C.
C8. the process according to Item C1, wherein the reaction conditions for the hydro-upgrading
unit include: a hydrogen partial pressure of about 5.0-20.0 MPa, a reaction temperature
of about 330-450 °C, a volume space velocity of about 0.1-3 h-1, and a hydrogen-to-oil volume ratio of about 300-3000.
C9. the process according to Item C1, wherein the catalyst used in the hydro-upgrading
unit comprises a hydrorefining catalyst and a hydrocracking catalyst, the hydrorefining
catalyst comprises a carrier and an active metal component selected from Group VIB
metals and/or Group VIII non-noble metals; the hydrocracking catalyst comprises a
zeolite, alumina, at least one Group VIII metal component and at least one Group VIB
metal component.
C10. the process according to Item C1, wherein, based on the weight of the catalyst,
the hydrocracking catalyst comprises 3-60 wt% of zeolite, 10-80 wt% of alumina, 1-15
wt% of nickel oxide and 5-40 wt% of tungsten oxide.
C11. the process according to Item C1, wherein the varied-diameter dilute-phase transport
bed comprises two reaction zones, and the ratio of the diameter of the second reaction
zone to that of the first reaction zone is 1.2-2.0: 1.
C12. the process according to Item C1, wherein the reaction conditions in the first
reaction zone of the varied-diameter dilute-phase transport bed include: a reaction
temperature of 500-620 °C, a reaction pressure of 0.2-1.2 MPa, a reaction time of
0.1-5.0 seconds, a weight ratio of catalyst to feedstock of 5-15, and a weight ratio
of steam to feedstock of 0.05-0.3: 1.
C13. the process according to Item C1, wherein the reaction conditions in the second
reaction zone of the varied-diameter dilute-phase transport bed include: a reaction
temperature of 450-550 °C, a reaction pressure of 0.2-1.2 MPa, and a reaction time
of 1.0-20.0 seconds.
C14. the process according to Item C1, wherein the catalyst contains, based on the
total weight of the catalyst, 1-60 wt% of a zeolite, 5-99 wt% of an inorganic oxide
and 0-70 wt% of clay, wherein the zeolite is selected from mesoporous zeolite and
optional macroporous zeolite, the mesoporous zeolite accounts for 50-100 wt% of the
total weight of the zeolite, and the macroporous zeolite accounts for 0-50 wt% of
the total weight of the zeolite.
C15. the process according to Item C14, wherein the mesoporous zeolite accounts for
70-100 wt% of the total weight of the zeolite and the macroporous zeolite accounts
for 0-30 wt% of the total weight of the zeolite.
C16. the process according to Item C1, wherein the pitch of step (2) is recycled to
step (1) for conversion reaction; or, the pitch obtained in step (2) is discarded;
or a part of the pitch obtained in step (2) is recycled to step (1) for conversion
reaction, and the rest of the pitch is discarded.
C17. the process according to Item C1, wherein the conversion rate of the conversion
reaction is about 30-70 wt%, the conversion rate of the conversion reaction = (weight
of components having a distillation range above 524 °C in the inferior oil - weight
of components having a distillation range above 524 °C in the conversion product)/weight
of components having a distillation range above 524 °C in the inferior oil ×100 wt%;
and/or the content of components having a distillation range between 350 °C and 524
°C in the heavy fraction is about 20-60 wt%.
C18. a system for producing propylene and high-octane gasoline from inferior oils,
comprising a conversion reaction unit, a vacuum distillation and/or extractive separation
unit, a hydro-upgrading unit and a catalytic cracking unit, wherein the conversion
reaction unit is connected to the vacuum distillation and/or extractive separation
unit, the vacuum distillation and/or extractive separation unit is connected to the
hydro-upgrading unit, and the hydro-upgrading unit is connected to the catalytic cracking
unit.
Examples
[0087] The present application will be described in further detail with reference to examples,
but is not limited thereto.
[0089] The following examples and comparative examples were carried out in accordance with
the embodiments shown in the drawings.
[0090] In the following examples and comparative examples, the inferior oil B used was a
vacuum residue, and its properties are shown in Table 1.
Table 1 Properties of feedstocks used in examples and comparative examples
| Name |
Inferior oil B |
| Density (20 °C)/(kg/m3) |
1060.3 |
| API degree |
1.95 |
| Carbon residue/wt% |
23.2 |
| Element content/wt% |
|
| Carbon |
84.62 |
| Hydrogen |
10.07 |
| Sulfur |
4.94 |
| Nitrogen |
0.34 |
| Oxygen |
/ |
| Four-component composition/wt% |
|
| Saturated component |
9.0 |
| Aromatic component |
53.8 |
| Resin |
24.5 |
| Asphaltenes |
12.7 |
| Metal content/(µg/g) |
|
| Ca |
2.4 |
| Fe |
23.0 |
| Ni |
42.0 |
| V |
96.0 |
| Content of components >524 °C/wt% |
100 |
Examples 1 and 3
[0091] On a medium-sized device, conversion reaction was carried out in a slurry bed reactor
using inferior oil B as a feedstock, followed by a first separation carried out in
two fractionating towers to obtain a first separated product and a second separated
product. The first separated product was subjected to a second separation (extractive
separation shown in Figs. 1b and 2b was performed in Example 1, and vacuum distillation
shown in Figs. 1a and 2a was performed in Example 3) to obtain an upgraded oil and
a pitch. The specific conditions and results of each step are shown in Table 2-1 and
Table 2-2.
Examples 2 and 4
[0092] On a medium-sized device, conversion reaction was carried out in a slurry bed reactor
using inferior oil B as a feedstock, followed by a first separation carried out in
two fractionating towers to obtain a first separated product and a second separated
product. The first separated product was subjected to a second separation (extractive
separation shown in Figs. 1b and 2b was performed in Example 2, and vacuum distillation
shown in Figs. 1a and 2a was performed in Example 4) to obtain an upgraded oil and
a pitch.
[0093] A part of the pitch obtained was recycled, and the rest was discarded. The recycled
pitch was mixed with the inferior oil B, and then subjected to conversion reaction,
followed sequentially by first separation and second separation to obtain an upgraded
oil and a pitch. The second separated product obtained was further separated to obtain
a naphtha fraction and an atmospheric gas oil. The specific conditions and results
of each step are shown in Table 2-1 and Table 2-2.
Comparative Example 1
[0094] The same basic procedure as in Example 1 was carried out, except that the conversion
reaction and the first separation were not conducted. The specific conditions and
results of each step are shown in Tables 2-1 and 2-2.
Comparative Example 2
[0095] The same basic procedure as in Example 2 was carried out, except that the conversion
reaction and the first separation were not conducted. The specific conditions and
results of each step are shown in Tables 2-1 and 2-2.
Comparative Example 3
[0096] The same basic procedure as in Example 2 was carried out, but the conversion catalyst
and operating conditions used were different. The specific conditions and results
of each step are shown in Tables 2-1 and 2-2.
Table 2-1 Reaction conditions used in examples and comparative examples
| |
Ex. 1 |
Ex. 2 |
Ex. 3 |
Ex. 4 |
Comp. Ex. 1 |
Comp. Ex. 2 |
Comp. Ex. 3 |
| Inferior oil feedstock |
Inferior oil B |
Inferior oil B |
Inferior oil B |
Inferior oil B |
Inferior oil B |
Inferior oil B |
Inferior oil B |
| Recycle of pitch |
No |
Yes |
No |
Yes |
No |
Yes |
Yes |
| Conversion reaction |
|
|
|
|
|
|
|
| Reaction temperature/ °C |
430 |
430 |
430 |
410 |
- |
- |
420 |
| Reaction pressure/MPa |
17 |
18 |
16 |
16 |
- |
- |
18 |
| Conversion catalyst (the values in parentheses are the wt% of the catalyst component) |
Ammonium molybdate |
Ammonium molybdate |
Molybdenum octoate |
Molybdenum naphthenate (75%) + nickel naphthenate (25%) |
- |
- |
Hematite |
| Volume space velocity/h-1 |
0.5 |
0.20 |
0.2 |
0.12 |
- |
- |
0.3 |
| Catalyst amount/(µg/g) |
1000 |
1000 |
1500 |
300 |
- |
- |
1500 |
| Hydrogen partial pressure/MPa |
15.8 |
17.1 |
15 |
15 |
- |
- |
17.4 |
| Volume ratio of hydrogen to inferior oil |
2000 |
1200 |
1200 |
1500 |
- |
- |
800 |
| First separation unit |
|
|
|
|
|
|
|
| First pressure/MPa |
17 |
17 |
16 |
16 |
- |
- |
18 |
| First temperature/ °C |
420 |
410 |
420 |
410 |
- |
- |
390 |
| Second pressure/MPa |
4.0 |
0.22 |
0.1 |
0.1 |
- |
- |
5.0 |
| Second temperature/ °C |
380 |
360 |
370 |
360 |
- |
- |
290 |
| Second separation unit |
|
|
|
|
|
|
|
| Extraction solvent |
n-C4H8 |
Catalytic cracking C3, C4 alkanes |
- |
- |
n-C4H8 |
n-C4H8 |
n-C4H8 |
| Operating temperature/ °C |
130 |
120 |
350 |
330 |
130 |
130 |
130 |
| Ratio of solvent (by mass) |
2.5 |
3.5 |
- |
- |
3.5 |
3.5 |
3.5 |
| Operating pressure/MPa |
4.0 |
5.0 |
Vacuum of 3mmHg |
Vacuum of 3mmHg |
4.0 |
4.0 |
4.0 |
∗Sources of each conversion catalyst are as follows:
Ammonium molybdate: Beijing reagent company, reagent pure grade;
Molybdenum octoate: a product prepared in laboratory, purity > 90%;
Molybdenum naphthenate: a product prepared in laboratory, purity > 85%;
Nickel naphthenate: a product prepared in laboratory, purity > 90%;
Hematite: an industrial product. |
Table 2-2 reaction results of examples and comparative examples
| Item |
Ex. 1 |
Ex. 2 |
Ex. 3 |
Ex. 4 |
Comp. Ex. 1 |
Comp. Ex. 2 |
Comp. Ex. 3 |
| Conversion rate of conversion reaction /% |
40.2 |
56.8 |
45.3 |
54.8 |
- |
- |
55.6 |
| Product distribution/wt% |
|
|
|
|
|
|
|
| First separated product |
55.3 |
69.4 |
80.7 |
88.7 |
- |
- |
70.4 |
| Content of components having a boiling point less than 350 °C in the first separated
product/wt% |
1 |
2 |
3.3 |
3 |
- |
- |
15 |
| Boiling point of the special component of the first separated product/°C. |
350-524 |
350-524 |
350-520 |
350-500 |
- |
- |
350-524 |
| Content of the special component in first separated product/wt% |
29 |
38 |
30 |
28 |
- |
- |
37 |
| End boiling point of second separated product/ °C |
334 |
348 |
342 |
345 |
- |
- |
285 |
| Upgrade result |
|
|
|
|
|
|
|
| Discard rate of pitch /%) |
51.6 |
5.2 |
37.5 |
6.9 |
65.8 |
74.9 |
17.6 |
| Conversion of inferior oil/%) |
48.4 |
94.8 |
62.5 |
93.1 |
34.2 |
25.1 |
82.4 |
| LPG + liquid product yield/%) |
45.6 |
89.5 |
55.7 |
84.5 |
34.2 |
25.1 |
78.2 |
| Heavy Metal content of upgraded oil /weight (µg/g) |
<1 |
<1 |
<1 |
<1 |
8 |
30 |
20 |
| Asphaltene content of upgraded oil /wt% |
<0.1 |
<0.1 |
<0.1 |
<0.1 |
1.5 |
3.2 |
2.8 |
| Yield of toluene insolubles/%) |
0.2 |
0.4 |
0.6 |
0.5 |
|
|
1.1 |
[0097] The results in Table 2-2 show that if the inferior oil is directly subjected to extractive
separation without conversion reaction, the yield of LPG + liquid product is only
34.2%, and the yield of pitch is 65.8%; if the pitch is recycled, the yield of LPG
+ liquid product is only 25.1% and the yield of pitch is as high as 74.9%.
[0098] In another aspect, the results of Comparative Example 3 show that when the content
of components having a boiling point less than 350 °C in the first separated product
is out of the range defined in the present application, the conversion rate of inferior
oil is decreased by 12% and the yield of LPG + liquid product is decreased by 11%,
while the heavy metal content of the upgraded oil reaches 20 µ g/g and the yield of
toluene insolubles is increased by about 1%.
Examples 5 to 6
[0099] The upgraded oils obtained in Examples 2 and 4 were respectively sent to a hydro-upgrading
unit, and subjected to hydro-upgrading at hydrofining and cracking temperatures of
380-386 °C, a volume space velocity of 0.5 h
-1, a hydrogen-to-oil volume ratio of 1000 and a hydrogen partial pressure of 15 MPa
to obtain a hydro-upgraded oil. The hydro-upgraded oil was simply separated to obtain
a hydro-upgraded heavy oil. Test conditions and properties of the hydro-upgraded heavy
oil are shown in Table 3.
Comparative Examples 4 to 5
[0100] Like in Examples 5-6, the upgraded oils obtained in Comparative Examples 1-2 were
subjected to hydro-upgrading to obtain a hydro-upgraded oil, and the hydro-upgraded
oil was simply separated to obtain a hydro-upgraded heavy oil. Test conditions and
properties of the hydro-upgraded heavy oil are shown in Table 3.
Table 3 Hydro-upgrading conditions and results for each example and comparative example
| Item |
Ex. 5 |
Ex. 6 |
Comp. Ex. 4 |
Comp. Ex. 5 |
| Source of hydro-upgraded |
Ex. 2 |
Ex. 4 |
Comp. Ex. |
Comp. Ex. |
| feedstock oil |
|
|
1 |
2 |
| Hydrorefining/cracking reaction temperature/°C |
380/380 |
382/383 |
384/385 |
385/386 |
| Trade name of hydrofining/cracking catalyst |
RN-410/RHC-131∗ |
| Total volume space velocity/h-1 |
0.5 |
0.5 |
0.5 |
0.5 |
| Hydrogen-to-oil volume ratio |
1000 |
1000 |
1000 |
1000 |
| Hydrogen partial pressure/MPa |
15 |
15 |
15 |
15 |
| Properties of hydro-upgraded heavy oil |
|
|
|
|
| Density (20 °C)/(kg/m3) |
890 |
895 |
901 |
903 |
| Sulfur/(µg/g) |
<200 |
<200 |
<200 |
<200 |
| Ni+V/(µg/g) |
<1 |
<1 |
<1 |
<1 |
| Hydrogen content/% |
12.90 |
12.86 |
12.70 |
12.65 |
| ∗Each hydrorefining/cracking catalyst is obtained from Sinopec Catalyst Co., Ltd. |
Examples 7 to 8
[0101] The hydro-upgraded heavy oils obtained in Example 5 and Example 6 were subjected
to catalytic cracking (reactor type as shown in Figs. 1a and 1 b) on a medium-size
device using a catalyst available from Qilu Catalyst Branch under the trade name CGP.
Preheated hydro-upgraded oil was fed to a first reaction zone of a varied-diameter
dilute-phase transport bed reactor and reacted under conditions including a reaction
temperature of 535 °C, a reaction time of 1.8 seconds, a catalyst-to-feedstock oil
weight ratio of 8, and a steam-to-feedstock oil weight ratio of 0.10. The oil-gas
mixture (vapor) and the catalyst flowed upward and entered a second reaction zone,
and further reaction was carried out under conditions including a reaction temperature
of 510 °C and a reaction time of 2.5 seconds. The reaction oil gas and the spent catalyst
were passed to a cyclone separator from the outlet of the reactor to allow a quick
separation of the reaction oil gas and the spent catalyst, and the reaction oil gas
was split in a separation system according to the distillation range to obtain fractions
such as propylene, gasoline and the like; the spent catalyst was passed to a steam
stripping section under the action of gravity to strip off hydrocarbon products adsorbed
on the spent catalyst by steam, and the stripped catalyst was passed to a regenerator
to contact with air for regeneration; the regenerated catalyst was passed to a degassing
tank to remove non-hydrocarbon gas impurities adsorbed on and carried by the regenerated
catalyst; the degassed regenerated catalyst was recycled to the varied-diameter dilute-phase
transport bed reactor for reuse. Operation conditions of the catalytic cracking unit
and product distribution are listed in Table 4.
[0102] As can be seen from the results in Table 4, for the hydro-upgraded heavy oil, the
propylene yield can reach 9.3 wt%, the gasoline yield can reach about 48.5 wt%, and
the octane number can reach as high as 98.2.
Comparative Examples 6 to 7
[0103] Substantially the same procedure as in Examples 7-8 was carried out, except that
the feedstocks were the hydro-upgraded heavy oils obtained in Comparative Examples
4-5, respectively. Operation conditions of the catalytic cracking unit and product
distribution are listed in Table 4.
[0104] As can be seen from the results in Table 4, for the hydro-upgraded heavy oil, the
propylene yield was only 6.2 wt%, the gasoline yield was only 35.8 wt%, and the octane
number was only 92.
Table 4 Catalytic cracking reaction conditions and results of Examples 7 to 8 and
Comparative Examples 6 to 7
| Item |
Ex. 7 |
Ex. 8 |
Comp. Ex. 6 |
Comp. Ex. 7 |
| Source of catalytic cracking feedstock oil (hydro-upgraded heavy oil) |
Ex. 5 |
Ex. 6 |
Comp. Ex. 4 |
Comp. Ex. 5 |
| First reaction zone of varied-diameter reactor |
|
|
|
|
| Reaction temperature/ °C |
535 |
535 |
535 |
535 |
| Reaction time/second |
1.8 |
1.8 |
1.8 |
1.8 |
| Weight ratio of catalyst to cracking feedstock |
8 |
8 |
8 |
8 |
| Weight ratio of steam to cracking feedstock |
0.1 |
0.1 |
0.1 |
0.1 |
| Second reaction zone of varied-diameter reactor |
|
|
|
|
| Reaction temperature/ °C |
510 |
510 |
510 |
510 |
| Reaction time/second |
2.5 |
2.5 |
2.5 |
2.5 |
| Catalytic cracking product distribution/wt% |
|
|
|
|
| Dry gas |
2.7 |
2.8 |
3.0 |
3.1 |
| Liquefied gas |
20.3 |
19.1 |
14.1 |
13.1 |
| Propylene therein |
9.4 |
9.3 |
6.2 |
6.0 |
| Gasoline |
47.8 |
48.5 |
35.8 |
35.2 |
| Diesel oil |
15.8 |
15.4 |
29.4 |
30.1 |
| Heavy oil |
4.4 |
4.7 |
8.4 |
8.9 |
| Coke |
9.0 |
9.5 |
9.3 |
9.6 |
| Research octane number of gasoline |
98 |
98.2 |
92 |
92.2 |
Examples 9 to 10
[0105] The hydro-upgraded heavy oils obtained in Example 5 and Example 6 were subjected
to catalytic cracking (reactor type as shown in Figs. 2a and 2b) on a medium-sized
device using a catalytic cracking catalyst available from Qilu Catalyst Branch under
the trade name MMC-2. Preheated hydro-upgraded oil was fed to a first reaction zone
of a combined catalytic cracking reactor, and subjected to cracking reaction under
conditions including an outlet temperature of the riser of 580 °C, a reaction time
of 1.8 seconds, a weight ratio of catalytic cracking catalyst to feedstock oil of
15, and a weight ratio of steam to feedstock oil of 0.25. The vapor and the catalyst
flowed upward and entered a second reaction zone, and further reaction was carried
out at a reaction temperature of 565 °C and a weight space velocity of catalyst bed
of 4h
-1. The reaction oil gas and the spent catalyst were passed to a shell type cyclone
separator from the outlet of the reactor to allow a quick separation of the reaction
oil gas and the spent catalyst, and the reaction oil gas was split in a separation
system according to the distillation range, to obtain fractions such as ethylene,
propylene, cracking gasoline and the like; the spent catalyst was passed to a steam
stripping section under the action of gravity to strip off hydrocarbon products adsorbed
on the spent catalyst by steam, and the stripped catalyst was passed to a regenerator
to contact with air for regeneration; the regenerated catalyst was passed to a degassing
tank to remove non-hydrocarbon gas impurities adsorbed on and carried by the regenerated
catalyst; the degassed regenerated catalyst was recycled to the riser reactor for
reuse. Operation conditions of the catalytic cracking unit and product distribution
are listed in Table 5.
[0106] As can be seen from the results in Table 5, for the hydro-upgraded heavy oil, the
yields of ethylene and propylene were 4.18 wt% and 20.50 wt%, respectively, and the
yield of light olefins (ethylene yield + propylene yield + butene yield, the same
applies hereinafter) was about 40.83%.
Comparative Examples 8 to 9
[0107] Substantially the same procedure as in examples 9-10 was carried out, except that
the feedstock was the hydro-upgraded heavy oils obtained in Comparative Examples 4-5.
Operation conditions of the catalytic cracking unit and product distribution are listed
in Table 5.
[0108] As can be seen from the results in Table 5, for the hydro-upgraded heavy oil, the
yields of ethylene and propylene were only 3.50 wt% and 19.87 wt%, respectively, and
the yield of light olefins (ethylene yield + propylene yield + butene yield, the same
applies hereinafter) was only 34.38%.
Table 5 Catalytic cracking reaction conditions and results of Examples 9 to 10 and
Comparative Examples 8 to 9
| Item |
Ex. 9 |
Ex. 10 |
Comp. Ex. 8 |
Comp. Ex. 9 |
| Source of catalytic cracking feedstock oil (hydro-upgraded heavy oil) |
Ex. 5 |
Ex. 6 |
Comp. Ex. 4 |
Comp. Ex. 5 |
| First reaction zone |
|
|
|
|
| Reaction temperature/ °C |
580 |
580 |
580 |
580 |
| Reaction time/second |
1.8 |
1.8 |
1.8 |
1.8 |
| Weight ratio of catalyst to cracking feedstock |
15 |
15 |
15 |
15 |
| Weight ratio of steam to cracking feedstock |
0.25 |
0.25 |
0.25 |
0.25 |
| Second reaction zone |
|
|
|
|
| Reaction temperature/ °C |
565 |
565 |
565 |
565 |
| Weight space velocity/h-1 |
4 |
4 |
4 |
4 |
| Catalytic cracking product distribution/wt% |
|
|
|
|
| H2-C2 (excluding ethylene) |
5.05 |
5.21 |
5.38 |
5.56 |
| Ethylene |
4.18 |
4.09 |
3.50 |
3.40 |
| C3-C4 (excluding propylene) |
20.9 |
20.38 |
19.87 |
19.37 |
| Propylene |
20.5 |
20.09 |
16.64 |
16.16 |
| C5+ gasoline |
27.08 |
27.49 |
28.41 |
28.84 |
| Cycle oil |
13.52 |
13.81 |
16.11 |
16.42 |
| Slurry oil |
1.31 |
1.35 |
1.39 |
1.43 |
| Coke |
7.46 |
7.58 |
8.70 |
8.82 |
| Light olefins/% |
40.83 |
39.96 |
34.38 |
33.42 |
Example 11
[0109] The light cycle oil fraction having a boiling range of less than 350 °C in the cycle
oil obtained in Example 10 was subjected to hydro-upgrading in the same manner as
in Example 6, along with the upgraded oil obtained in Example 4. The hydro-upgrading
conditions and product properties are shown in Table 6.
Table 6 Hydro-upgrading conditions and results for Example 11
| Item |
Example 11 |
| Hydro-upgrading feedstock oil |
Light cycle oil of Example 10 + upgraded oil of Example 4 |
| Feedstock ratio (light cycle oil/upgraded oil) |
0.42 |
| Hydro-upgrading conditions |
|
| Hydrorefining/cracking reaction temperature/°C |
382/383 |
| Hydrogen partial pressure/MPa |
15.0 |
| Trade name of hydrofining/cracking catalyst |
RN-410/RHC-131 |
| Volume space velocity/h-1 |
0.5 |
| Hydrogen-to-oil volume ratio |
1000 |
| Properties of hydro-upgraded heavy oil |
|
| Density (20 °C)/(kg/m3) |
895.0 |
| Sulfur/(µg/g) |
<200 |
| Ni+V/(µg/g) |
<1 |
| Hydrogen content/% |
12.86 |
Examples 12 to 13
[0110] The hydro-upgraded heavy oil obtained in Example 11 was subjected to catalytic cracking
in a conventional riser reactor, the catalytic cracking catalyst was obtained from
Qilu Branch of Sinopec Catalyst Co., Ltd.. The catalytic cracking conditions and results
are shown in Table 7.
[0111] As can be seen from the results in Table 7, when the light cycle oil and the upgraded
oil are subjected to hydro-upgrading to obtain a hydro-upgraded heavy oil, and then
the hydro-upgraded heavy oil is subjected to catalytic cracking to produce light olefins
such as ethylene and propylene, the yield of light olefins of Example 12 can reach
36.22%, and the yield of light olefins of Example 13 can reach 36.92%.
Table 7 Catalytic cracking reaction conditions and results for Examples 12-13
| Item |
Example 12 |
Example 13 |
| Source of hydrocracking feedstock oil (hydro-upgraded heavy oil) |
Example 11 |
| Catalytic cracking conditions |
|
|
| Trade name of catalyst |
MMC-2 |
CEP-1 |
| Reaction temperature/ °C |
565 |
620 |
| Reaction time/second |
3 |
2.5 |
| Reaction pressure/MPa |
0.15 |
0.15 |
| Weight ratio of catalyst to cracking feedstock |
15.0 |
20 |
| Weight ratio of steam to cracking feedstock |
0.25 |
0.3 |
| Catalytic cracking product distribution/wt% |
|
|
| H2-C2 (excluding ethylene) |
5.21 |
12.14 |
| Ethylene |
4.09 |
12.59 |
| C3-C4 (excluding propylene) |
20.38 |
6.65 |
| Propylene |
20.09 |
19.67 |
| C5+ gasoline |
27.49 |
19.42 |
| Cycle oil |
13.81 |
7.33 |
| Slurry oil |
1.35 |
10.26 |
| Coke |
7.58 |
11.94 |
| Yield of light olefins/% |
36.22 |
36.92 |
Example 14
[0112] An experiment was carried out like in Example 2 on a pilot plant, in which the slurry
oil obtained in Example 10 was recycled, and mixed with the inferior oil B and the
recycled pitch for conversion reaction, and then the conversion product was subjected
to a first separation to obtain a first separated product and a second separated product.
The first separated product was subjected to a second separation (extractive separation)
to obtain an upgraded oil and a pitch. A part of the pitch was recycled, and the rest
was discarded. Operating conditions of each step were the same as in Example 2, and
the results are shown in Table 8.
[0113] The results in Table 8 show that the conversion rate of the inferior oil and the
yield of LPG + liquid product are increased by 1.6% and 1.3%, respectively, through
the recycle of the slurry oil, and the yield of toluene insolubles is reduced by 50%.
Table 8 Comparison of results of Examples 2 and 14
| Item |
Example 2 |
Example 14 |
| Inferior oil feedstock (values shown in parentheses are weight percentages) |
Inferior oil B |
Inferior oil B (90) + slurry oil (10) |
| Source of slurry oil |
- |
Example 10 |
| Recycle of pitch |
Yes |
Yes |
| Conversion rate of conversion reaction/wt% |
56.8 |
53.7 |
| Product distribution/wt% |
|
|
| First separated product |
69.4 |
76.6 |
| Content of the special component in the first separated product/wt% |
38 |
42 |
| Content of components having a boiling point less than 350 °C in the first separated
product/wt% |
2 |
1 |
| Second separated product |
25.8 |
18.6 |
| End boiling point of second separated product/ °C |
348 |
350 |
| Upgrading results |
|
|
| Conversion rate of inferior oil/wt% |
94.8 |
96.4 |
| Discard rate of pitch/wt% |
5.2 |
3.6 |
| Yield of LPG + liquid product/wt% |
89.5 |
90.8 |
| Heavy metal content of upgraded oil/weight (µg/g) |
<1 |
<1 |
| Asphaltene content of upgraded oil/wt% |
<0.1 |
<0.1 |
| Yield of toluene insolubles/wt% |
0.4 |
0.2 |
[0114] The results of the examples show that the process and system of the present application
can greatly improve the yield of LPG + liquid product obtained by upgrading of inferior
oils, improve the quality of feedstock for catalytic cracking unit, and have the advantages
of high yields of ethylene and propylene and high yield of high-octane gasoline.
[0115] The present application is illustrated in detail hereinabove with reference to preferred
embodiments, but is not intended to be limited to those embodiments. Various modifications
may be made following the inventive concept of the present application, and these
modifications shall be within the scope of the present application.
[0116] It should be noted that the various technical features described in the above embodiments
may be combined in any suitable manner without contradiction, and in order to avoid
unnecessary repetition, various possible combinations are not described in the present
application, but such combinations shall also be within the scope of the present application.
[0117] In addition, the various embodiments of the present application can be arbitrarily
combined as long as the combination does not depart from the spirit of the present
application, and such combined embodiments should be considered as the disclosure
of the present application.
1. A process for producing light olefins from inferior oils, comprises the steps of:
1) subjecting an inferior oil feedstock to a thermal conversion reaction in the presence
of hydrogen to obtain a conversion product;
2) subjecting the conversion product to a first separation to obtain a first separated
product, wherein the first separated product has a content of components having a
boiling point below 350 °C of not greater than about 5 wt%, preferably less than about
3 wt%, and a content of components having a boiling point between 350 °C and 524 °C
of about 20-60 wt%, preferably about 25-55 wt%;
3) subjecting the first separated product to a second separation to obtain an upgraded
oil and a pitch, wherein the second separation is selected from the group consisting
of vacuum distillation, solvent extraction, or a combination thereof;
4) subjecting the upgraded oil obtained in step 3) to hydro-upgrading to obtain a
hydro-upgraded oil;
5) subjecting the hydro-upgraded oil obtained in step 4) to a third separation to
obtain a hydro-upgraded heavy oil;
6) subjecting the hydro-upgraded heavy oil obtained in step 5) to catalytic cracking
to obtain a catalytic cracking product comprising a light olefin; and
7) optionally, recycling at least a part of the pitch obtained in step 3) to step
1) for the thermal conversion reaction.
2. The process according to claim 1, wherein the thermal conversion reaction of step
1) is conducted in a slurry bed reactor.
3. The process according to any one of the preceding claims, wherein the thermal conversion
reaction of step 1) is carried out in the presence of hydrogen and a conversion catalyst,
wherein the conversion catalyst comprises at least one compound selected from the
group consisting of Group VB metal compounds, Group VIB metal compounds and Group
VIII metal compounds.
4. The process according to any one of the preceding claims, wherein the thermal conversion
reaction of step 1) is carried out under conditions including:
a temperature of about 380-470 °C, a hydrogen partial pressure of about 10-25 MPa,
a volume space velocity of the inferior oil of about 0.01-2 h-1, a volume ratio of hydrogen to the inferior oil of about 500-5000, and an amount
of the conversion catalyst of about 10-50000 µg/g calculated on the basis of the active
metal in the conversion catalyst and relative to the weight of the inferior oil.
5. The process according to any one of the preceding claims, wherein the inferior oil
is at least one selected from the group consisting of inferior crude oil, heavy oil,
deoiled asphalt, coal derived oil, shale oil, and petrochemical waste oil,
preferably, the inferior oil satisfies one or more of the following criteria: an API
degree of less than about 27, a boiling point greater than about 350 °C, an asphaltene
content greater than about 2 wt%, and a heavy metal content greater than about 100
µg/g, calculated as the total weight of nickel and vanadium.
6. The process according to any one of the preceding claims, wherein the thermal conversion
reaction of step 1) is carried out to an extent that a conversion rate of about 30-70
wt% is obtained, wherein the conversion rate = (weight of components having a boiling
point above 524 °C in the inferior oil - weight of components having a boiling point
above 524 °C in the conversion product)/weight of components having a boiling point
above 524 °C in the inferior oil ×100 wt%;
preferably, said thermal conversion reaction of step 1) is carried out to an extent
that a conversion rate of about 30-60 wt% is obtained.
7. The process according to any one of the preceding claims, wherein the first separating
of step 2) comprises:
2a) separating the conversion product obtained in step 1) at a first pressure and
a first temperature to obtain a gas component and a liquid component; and
2b) separating the resulting liquid component at a second pressure and a second temperature
to yield the first separated product and a second separated product, wherein the first
pressure is greater than the second pressure,
preferably, the first pressure is about 10-25 MPa, and the first temperature is about
380-470 °C; the second pressure is about 0.1-5 MPa, and the second temperature is
about 150-390 °C.
8. The process according to claim 7, wherein the first separating of step 2) further
comprises:
2c) splitting at least a part of the second separated product obtained in step 2b)
to obtain a naphtha and an atmospheric gas oil;
2d) recycling at least a part of the gas component obtained in step 2a) to step 1)
for the thermal conversion reaction; and/or
2e) recycling at least a part of the gas component obtained in step 2a) to step 4)
for the hydro-upgrading.
9. The process according to claim 8, further comprising:
2f) recycling at least a part of the second separated product obtained in step 2b)
and/or at least a part of the atmospheric gas oil obtained in step 2c) to step 4)
for hydro-upgrading together with the upgraded oil.
10. The process according to any one of the preceding claims, wherein the hydro-upgrading
of step 4) is carried out under conditions including:
a hydrogen partial pressure of about 5.0-20.0 MPa, a reaction temperature of about
330-450 °C, a volume space velocity of about 0.1-3 h-1, and a hydrogen-to-oil volume ratio of about 300-3000.
11. The process according to any one of the preceding claims, wherein the hydro-upgrading
of step 4) is carried out in the presence of a hydrorefining catalyst and/or a hydrocracking
catalyst, the hydrorefining catalyst comprises a carrier and an active metal component
selected from Group VIB metals and/or Group VIII non-noble metals; the hydrocracking
catalyst comprises a zeolite, alumina, at least one Group VIII metal component and
at least one Group VIB metal component,
preferably, the hydrorefining catalyst comprises, based on the dry weight of the hydrorefining
catalyst, about 30-80 wt% of an alumina carrier, about 5-40 wt% of molybdenum oxide,
about 5-15 wt% of cobalt oxide and about 5-15 wt% of nickel oxide; the hydrocracking
catalyst comprises, based on the dry weight of the hydrocracking catalyst, about 3-60
wt% of a zeolite, about 10-80 wt% of alumina, about 1-15 wt% of nickel oxide, and
about 5-40 wt% of tungsten oxide.
12. The process according to any one of claims 1-11, wherein the catalytic cracking of
step 6) is carried out in a varied-diameter dilute-phase transport bed reactor and/or
a combined catalytic cracking reactor,
wherein the varied-diameter dilute-phase transport bed reactor comprises, from bottom
to top, a first reaction zone and a second reaction zone having different diameters,
the ratio of the diameter of the second reaction zone to the diameter of the first
reaction zone is from about 1.2 : 1 to about 2.0 : 1; the combined catalytic cracking
reactor comprises, from bottom to top, a first reaction zone and a second reaction
zone, wherein the first reaction zone is a riser reactor, and the second reaction
zone is a fluidized bed reactor.
13. The process according to claim 12, wherein:
in the varied-diameter dilute-phase transport bed reactor, the reaction conditions
in the first reaction zone include: a reaction temperature of about 500-620 °C, a
reaction pressure of about 0.2-1.2MPa, a reaction time of about 0.1-5.0 seconds, a
weight ratio of catalyst to cracking feedstock of about 5-15, and a weight ratio of
steam to cracking feedstock of about 0.05 : 1 to about 0.3 : 1; and the reaction conditions
in the second reaction zone include: a reaction temperature of about 450-550 °C, a
reaction pressure of about 0.2-1.2MPa, a reaction time of about 1.0-20.0 seconds,
and/or
in the combined catalytic cracking reactor, the reaction conditions in the first reaction
zone include: a reaction temperature of about 560-750 °C, a reaction time of about
1-10 seconds, and a catalyst-oil ratio of about 1 : 1 to about 50 : 1; and the reaction
conditions in the second reaction zone include: a reaction temperature of about 550-700
°C, and a weight space velocity of about 0.5-20 h -1 .
14. The process according to any one of the preceding claims, wherein the catalytic cracking
of step 6) is conducted in the presence of a catalytic cracking catalyst comprising,
based on the weight of the catalyst, about 1-60 wt% of a zeolite, about 5-99 wt% of
an inorganic oxide, and about 0-70 wt% of clay, and wherein the zeolite comprises
about 50-100 wt%, preferably about 70-100 wt%, of a mesoporous zeolite, and about
0-50 wt%, preferably about 0-30 wt%, of a macroporous zeolite, based on the total
weight of the zeolite.
15. The process according to any one of the preceding claims, wherein:
the second separation of step 3) is a vacuum distillation, and the vacuum distillation
is carried out at a vacuum degree of about 1-20 mmHg and a temperature of about 250-350
°C; or
alternatively, the second separation of step 3) is a solvent extraction carried out
under conditions including: a pressure of about 3-12 MPa, preferably about 3.5-10
MPa; a temperature of about 55-300 °C, preferably about 70-220 °C; an extraction solvent
of C3-C7 hydrocarbon, preferably at least one of C3-C5 alkanes and C3-C5 alkenes, and further preferably at least one of C3-C4 alkanes and C3-C4 alkenes; a weight ratio of extraction solvent to the first separated product of about
1 : 1 to about 7 : 1, preferably about 1.5 : 1 to about 5 : 1; or
alternatively, the second separation of step 3) is a combination of vacuum distillation
and extractive separation, of which the conditions are as defined above.
16. The process according to any one of the preceding claims, wherein in step 7) about
30-95 wt%, preferably about 50-90 wt% of the pitch obtained in step 3) is recycled
to step 1) for the thermal conversion reaction,
preferably, the pitch has a softening point of less than about 150 °C.
17. The process according to any one of the preceding claims, wherein the third separation
of step 5) comprises splitting the hydro-upgraded oil into a hydro-upgraded light
oil and a hydro-upgraded heavy oil, and the split point between the hydro-upgraded
light oil and the hydro-upgraded heavy oil is about 340-360 °C, preferably about 345-355
°C, more preferably about 350°C.
18. A system for producing light olefins from inferior oils, comprising a thermal conversion
reaction unit, a first separation unit, a second separation unit, a hydro-upgrading
unit, a third separation unit and a catalytic cracking unit, wherein:
the thermal conversion reaction unit is configured to carry out a thermal conversion
reaction on an inferior oil feedstock in the presence of hydrogen to obtain a conversion
product;
the first separation unit is configured to separate the conversion product to obtain
a first separated product, in which the content of components having a boiling point
below 350 °C is not greater than about 5 wt%, preferably less than about 3 wt%, and
the content of components having a boiling point between 350 °C and 524 °C is about
20-60 wt%, preferably about 25-55 wt%;
the second separation unit is configured to separate the first separated product into
an upgraded oil and a pitch, and is selected from the group consisting of vacuum distillation
unit, solvent extraction unit or a combination thereof;
the hydro-upgrading unit is configured to carry out hydro-upgrading reaction on the
upgraded oil to obtain a hydro-upgraded oil;
the third separation unit is configured to separate the hydro-upgraded oil to obtain
a hydro-upgraded heavy oil; and
the catalytic cracking unit is configured to carry out catalytic cracking reaction
on the hydro-upgraded heavy oil to obtain a catalytic cracking product comprising
a light olefin.
19. The system according to claim 18, wherein the thermal conversion reaction unit comprises
a slurry bed reactor.
20. The system according to claim 18 or 19, wherein the catalytic cracking unit comprises
a varied-diameter dilute-phase transport bed reactor and/or a combined catalytic cracking
reactor consisting of a riser reactor and a fluidized bed reactor.